Polymer compositions having improved properties of thermal stability, color, and/or flow

ABSTRACT

This invention relates to a polymer composition comprising:
         (A) at least one polymer comprising at least one diol residue, and   (B) a stabilizer composition comprising:
           (1) at least one primary antioxidant comprising at least one phenolic antioxidant; and   (2) at least one secondary antioxidant comprising at least one phosphite, and   (3) at least one chain extending agent;
 
wherein the b* value for said polymer composition is less than 10 according to the L*, a* and b* color system of the CIE (International Commission on Illumination) after being heated for at least three hours at 200° C. or 24 hours at 175° C.

FIELD OF THE INVENTION

This invention relates to combinations of additives to improve thermaloxidative stability, color properties, and/or flow of condensationpolymers.

BACKGROUND OF THE INVENTION

Polyesters and other polymeric materials degrade during processing andusage due to exposures such as heat, processing time, storage time,ultraviolet light, or other potential conditions.

There are two main types of antioxidants, referred to as primary andsecondary, and defined by their mode of operation. Primary antioxidantsare free radical scavengers that generally terminate free radical chainpropagation by donating a hydrogen atom. In one embodiment, primaryantioxidants can include hindered phenols and secondary aromatic amines.Secondary antioxidants are hydroperoxide radical decomposers thatoperate by decomposing the radical into stable non-reactive products andare typically divalent sulfur or trivalent phosphorous.

Combinations of primary antioxidants and secondary antioxidants havebeen previously used to improve stability of thermoplastic materialsduring processing and throughout their service life. However, even withthe use of these additives, there is room for improvement in thestability of these materials during processing and service life.

In fact, there is a need in the art for polymeric material that hasimproved oxidative stability, improved hydrolytic stability and/orimproved viscosity, as well as other improved properties, for use invarious applications, e.g., after being heated at elevated temperaturesand/or for time periods greater than typically needed for standardmolding and extrusion processes. Examples of these applications are 3Dprinting and Light Emitting Diodes (LED).

SUMMARY OF THE INVENTION

In one aspect of the invention, the polymer compositions of theinvention demonstrate improved properties, including but not limited to:improved thermal oxidative stability, improved hydrolytic stability,lower zero shear viscosity, molecular weight stability, inherentviscosity stability, improved color stability, melt viscosity stability,lower number of carboxyl end groups, and/or combinations of two or morethese properties.

These benefits can be useful in various applications, e.g., processesrequiring elevated temperatures. In one aspect, combinations of aprimary antioxidant, a secondary antioxidant, and a chain extendingadditive unpredictably inhibit the thermal oxidative degradation whilesimultaneously greatly improving the color stability of polymers heldbelow their melting point and maximum processing temperature.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one thermoplastic polymer, and    -   (B) a stabilizer composition comprising:        -   (1) at least one primary antioxidant;        -   (2) at least one secondary antioxidant; and        -   (3) at least one chain extending agent.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one condensation polymer, and    -   (B) a stabilizer composition comprising:        -   (1) at least one phenolic antioxidant;        -   (2) at least one phosphite; and        -   (3) at least one chain extending agent.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polymer selected from liquid crystalline        polyesters/amides/imides, polyesteramides, polyimides,        polyetherimides, polyurethanes, polyureas, polybenzimidazole,        polybenzoxazoles, polyimines, polycarbonates, polyesters,        copolyesters, and polyamides; and    -   (B) a stabilizer composition comprising:        -   (1) at least one primary antioxidant;        -   (2) at least one secondary antioxidant; and        -   (3) at least one chain extending agent.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polymer selected from thermoplastic polymers,        condensation polymers, polyesters, amorphous polyesters,        semi-crystalline polyesters, polyamides, or any of the foregoing        polymers, comprising residues of cyclohexanedimethanol (e.g.,        1,4-cyclohexanedimethanol); and    -   (B) a stabilizer composition comprising:        -   (1) at least one primary antioxidant;        -   (2) at least one secondary antioxidant; and        -   (3) at least one chain extending agent.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polyester, and    -   (B) a stabilizer composition comprising:        -   (1) at least one primary antioxidant;        -   (2) at least one secondary antioxidant; and        -   (3) at least one chain extending agent.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polymer selected from polyesters (including but        not limited to polyesterethers), polyamides, and comprising or        not comprising residues of cyclohexanedimethanol (e.g.,        1,4-cyclohexanedimethanol); and    -   (B) a stabilizer composition comprising:        -   (1) at least one hindered phenolic antioxidant;        -   (2) at least one phosphite antioxidant; and        -   (3) at least one chain extending agent comprising at least            one copolymer of glycidyl methacrylate and styrene.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polyester comprising cyclohexanedimethanol,        e.g. 1,4-cyclohexanedimethanol, and    -   (B) a stabilizer composition comprising:        -   (1) at least one primary antioxidant;        -   (2) at least one secondary antioxidant; and        -   (3) at least one chain extending agent.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polyester comprising cyclohexanedimethanol,        e.g. 1,4-cyclohexanedimethanol, and    -   (B) a stabilizer composition comprising:        -   (1) at least one phenolic antioxidant; and        -   (2) at least one phosphite; and        -   (3) at least one chain extending agent.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polymer selected from thermoplastic polymers,        condensation polymers, polyesters, amorphous polyesters,        semi-crystalline polyesters, crystalline polyesters, polyamides,        or any of the foregoing polymers, comprising residues of        cyclohexanedimethanol (e.g., 1,4-cyclohexanedimethanol); and    -   (B) a stabilizer composition comprising:        -   (1) at least one phenolic antioxidant;        -   (2) at least one phosphite; and        -   (3) at least one multifunctional epoxy containing chain            extending agent comprising, for example, from at least 2 or            at least 3 or at least 4 or at least 5 functional epoxy            groups, etc., or from 2 to 18 functional epoxy groups, or            from 2 to 10 functional epoxy groups or from 3 to 8            functional epoxy groups.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polymer selected from liquid crystalline        polyesters/amides/imides, polyesteramides, polyimides,        polyetherimides, polyurethanes, polyureas, polybenzimidazole,        polybenzoxazoles, polyimines, polycarbonates, polyesters,        copolyesters, and polyamides;    -   (B) a stabilizer composition comprising:        -   (1) at least one phenolic antioxidant;        -   (2) at least one phosphite; and        -   (3) at least one multifunctional epoxy containing chain            extending agent comprising, for example, from at least 2 or            at least 3 or at least 4 or at least 5 functional epoxy            groups, etc., or from 2 to 18 functional epoxy groups, or            from 2 to 10 functional epoxy groups or from 3 to 8            functional epoxy groups.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polyester comprising residues of        1,4-cyclohexanedimethanol, and    -   (B) a stabilizer composition comprising:        -   (1) at least one phenolic antioxidant;        -   (2) at least one phosphite; and        -   (3) at least one multifunctional epoxy containing chain            extending agent, for example, 2-20 functional epoxy groups            or 3-15 functional groups or 3-8 functional groups.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polyester, and    -   (B) a stabilizer composition comprising:        -   (1) at least one phenolic antioxidant;        -   (2) at least one phosphite; and        -   (3) at least one copolymer of glycidyl methacrylate with            styrene.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polyester comprising residues of        1,4-cyclohexanedimethanol, and    -   (B) a stabilizer composition comprising:        -   (1) at least one phenolic antioxidant;        -   (2) at least one phosphite; and        -   (3) at least one copolymer of glycidyl methacrylate with            styrene.

In one aspect, there is provided a polymer composition comprising:

-   -   (A) at least one polymer selected from polyesters (including but        not limited to polyesterethers), optionally comprising residues        of cyclohexanedimethanol (e.g., 1,4-cyclohexanedimethanol) and        from polyamides;    -   (B) a stabilizer composition comprising:        -   (1) at least hindered phenolic antioxidant;        -   (2) at least one phosphite antioxidant; and        -   (3) at least one chain extending agent comprising at least            one copolymer of glycidyl methacrylate with styrene.

In one embodiment, the invention relates to a method for stabilizing anyof the thermoplastic polymers useful in the invention against surfaceoxidative degradation, comprising: incorporating into the polymer aneffective stabilizing amount of the stabilizer composition of theinvention.

For certain aspects of the invention, the polymer composition can haveimproved properties, for example, for color stability, thermal oxidativestability, melt viscosity stability, inherent viscosity stability, zeroshear viscosity, and/or melt stability as can be expressed in number ofcarboxyl end groups.

In certain aspects, the improvements observed were unpredictable andgreater than would be expected from the sum of the individual effects ofeach additive on the polymer and/or greater than what would be expectedfrom other combinations of additives, such as combinations of primaryantioxidants and secondary antioxidants without the chain extendingagents.

DESCRIPTION OF THE FIGURES

FIG. 1: The graph in FIG. 1 shows melt flow as a function of temperaturefor a PCTA polymer used for calculation of the degree of crystallizationfor that polymer.

FIG. 2-FIG. 6: FIGS. 2 to 6 show the effect of oven aging samples at 170C up to 20 hours without any anti-oxidants (Example 25-1), with only aconventional antioxidant combination (Runs 25-2, -3 and -4) and with thetricombination of antioxidant additives (Runs 25-5, -6, and -7).

FIG. 7: The plot in FIG. 7 shows the effect on inherent viscosity atdifferent levels of primary antioxidant (Irganox™1010 antioxidant),secondary antioxidant (Irgafos™ 168 antioxidant) and chain extendingagent (Joncryl™4468 additive) for Polyester 2.

FIG. 8: The plot in FIG. 8 shows the effect on carboxyl end groups (CEG)at different levels of primary antioxidant (Irganox™1010 antioxidant),secondary antioxidant (Irgafos™ 168 antioxidant) and chain extendingagent (Joncryl™4468 additive) for Polyester 2.

FIG. 9: The plot in FIG. 9 shows the effect on initial b*color atdifferent levels of primary antioxidant (Irganox™1010 antioxidant),secondary antioxidant (Irgafos™168 antioxidant) and chain extendingagent (Joncryl™4468 additive) for Polyester 2.

FIG. 10: The plot in FIG. 10 shows the effect on aged/final b*color atdifferent levels of primary antioxidant (Irganox™1010 antioxidant),secondary antioxidant (Irgafos™ 168 antioxidant) and chain extendingagent (Joncryl™4468 additive) for Polyester 2.

FIG. 11: Desirability plot for targets of stable IV, low CEG, lowinitial b*, and low final b* (with Irgafos™168 concentration of 0.5%).

FIG. 12: Contour Overlay Plot of optimum compositions with Irgafos™168concentration of 0.25%.

FIG. 13: Contour Overlay Plot of optimum compositions with Irgafos™168concentration of 0.5%.

DETAILED DESCRIPTION

The present invention may be understood more readily by reference to thefollowing detailed description of certain embodiments of the inventionand the working examples. In accordance with the purpose(s) of thisinvention, certain embodiments of the invention are described in theSummary of the Invention and are further described herein below. Also,other embodiments of the invention are described herein.

The present invention involves the use of primary antioxidants,secondary antioxidants and chain extending additives which can inhibitthe thermal oxidative and hydrolytic degradation of polymers, optionallyheld at elevated temperatures for extended periods of time and canimprove polymer flow.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, reaction conditions,and so forth used in the specification and claims are to be understoodas being modified in all instances by the term “about.” Accordingly,unless indicated to the contrary, the numerical parameters set forth inthe following specification and attached claims are approximations thatmay vary depending upon the desired properties sought to be obtained bythe present invention. At the very least, each numerical parametershould at least be construed in light of the number of reportedsignificant digits and by applying ordinary rounding techniques.Further, the ranges stated in this disclosure and the claims areintended to include the entire range specifically and not just theendpoint(s). For example, a range stated to be 0 to 10 is intended todisclose all whole numbers between 0 and 10 such as, for example 1, 2,3, 4, etc., all fractional numbers between 0 and 10, for example 1.5,2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10. Also, a rangeassociated with chemical substituent groups such as, for example, “C₁ toC₅ hydrocarbons,” is intended to specifically include and disclose C₁and C₅ hydrocarbons as well as C₂, C₃, and C₄ hydrocarbons.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

As used in the specification and the claims, the singular forms “a,”“an” and “the” include their plural references unless the contextclearly dictates otherwise. References to a composition or processcontaining or including “an” ingredient or “a” step is intended toinclude other ingredients or other steps, respectively, in addition tothe one named.

The terms “containing” or “including,” are synonymous with the term“comprising,” and is intended to mean that at least the named compound,element, particle, or method step, etc., is present in the compositionor article or method, but does not exclude the presence of othercompounds, catalysts, materials, particles, method steps, etc., even ifthe other such compounds, material, particles, method steps, etc., havethe same function as what is named, unless expressly excluded in theclaims.

It is also to be understood that the mention of one or more method stepsdoes not preclude the presence of additional method steps before orafter the combined recited steps or intervening method steps betweenthose steps expressly identified. Moreover, the lettering of processsteps or ingredients is a convenient means for identifying discreteactivities or ingredients and the recited lettering can be arranged inany sequence, unless otherwise indicated.

In each embodiment of the invention, the polymers useful in theinvention can comprise condensation polymers. Condensation polymersuseful in the invention can include but are not limited to, at least oneof liquid crystalline polyesters/amides/imides, polyesteramides,polyimides, polyetherimides, polyurethanes, polyureas,polybenzimidazole, polybenzoxazoles, polyimines, polycarbonate,polyesters, copolyesters, polyamides (e.g., Nylon 6,6 or Nylon 6), ormixtures thereof. All of these polymers can be susceptible to thermaloxidative and hydrolytic degradation. Polycaprolactone, polycaprolactam,while not typically synthesized using condensation polymerization, arealso susceptible to hydrolytic degradation and are included within thescope of this invention. Polyphenylene sulfide, polyphenylene oxide,poly ether ether ketone, poly ether ketone, poly ether ketone ketone,while not condensation polymers in the traditional sense, are highlysusceptible to cross-linking and branching during melt processing andthey are limited by thermal stability during processing and end useapplications in the oil and gas industries and are included within thescope of this invention. The polymers useful in the polymer compositionof the invention can be thermoplastic.

In one embodiment, the polymer composition useful in the inventioncomprises at least one polyester. In embodiments, polyesters useful inthe present invention can comprise residues of at least one aromaticdiacid and residues of at least one glycol. The term “copolyester,” asused herein, is intended to include “polyesters” and is understood tomean a synthetic polymer prepared by the reaction of one or moredifunctional carboxylic acids and/or multifunctional carboxylic acidswith one or more difunctional hydroxyl compounds and/or multifunctionalhydroxyl compounds. Typically, the difunctional carboxylic acid can be adicarboxylic acid and the difunctional hydroxyl compound can be adihydric alcohol such as, for example, glycols. Furthermore, as used inthis application, the interchangeable terms “diacid” or “dicarboxylicacid” include multifunctional acids, such as branching agents. The term“glycol” as used in this application includes, but is not limited to,diols, glycols, and/or multifunctional hydroxyl compounds.Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid such as, for example, p-hydroxybenzoic acid, and thedifunctional hydroxyl compound may be an aromatic nucleus bearing 2hydroxyl substituents such as, for example, hydroquinone. The term“residue,” as used herein, means any organic structure incorporated intoa polymer through a polycondensation and/or an esterification reactionfrom the corresponding monomer. The term “repeating unit,” as usedherein, means an organic structure having a dicarboxylic acid residueand a diol residue bonded through an ester group. Thus, for example, thedicarboxylic acid residues may be derived from a dicarboxylic acidmonomer or its associated acid halides, esters, half-esters, salts,half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful ina reaction process with a diol to make polyester. As used herein, theterm “terephthalic acid” is intended to include terephthalic acid itselfand residues thereof as well as any derivative of terephthalic acid,including its associated acid halides, esters, half-esters, salts,half-salts, anhydrides, mixed anhydrides, or mixtures thereof orresidues thereof useful in a reaction process with a diol to makepolyester. The term “modifying aromatic diacid” means an aromaticdicarboxylic acid other the terephthalic acid. The term “modifyingglycol” means a glycol other than 1,4-cyclohexanedimethanol. In oneembodiment, terephthalic acid may be used as the starting material. Inanother embodiment, dimethyl terephthalate may be used as the startingmaterial. In another embodiment, mixtures of terephthalic acid anddimethyl terephthalate may be used as the starting material and/or as anintermediate material. For the purposes of this invention,polyesterethers are included within the definition of polyesters withinthe scope of this invention.

The polyesters and copolyesters of the present invention are readilyprepared by methods well known in the art, for example, as described inU.S. Pat. No. 2,012,267, incorporated herein by reference in itsentirety. More particularly, the reactions for preparing thecopolyesters are usually carried out at temperatures of about 150° C. toabout 300° C. in the presence of polycondensation catalysts such astitanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tindiacetate, zinc chloride, or combinations thereof. The catalysts aretypically employed in amounts of 10 to 1000 ppm, based on total weightof the reactants.

In one embodiment, the polymer composition useful in the invention cancontain at least one polymer comprising cyclohexanedimethanol, e.g.1,4-cyclohexanedimethanol. In one embodiment, the polymer compositionuseful in the invention can contain at least one polymer comprisingethylene glycol.

Condensation polymers are also susceptible to hydrolytic degradation ifnot pre-dried or if they are held at elevated temperatures in moist airfor a long period of time. Condensation polymers are any polymers wheremonomers reacting during polycondensation to create a polymer and aby-product such as water or methanol is produced. The polymerizationreaction is reversible; thus, condensation polymers are often pre-driedbefore processing.

The polyesters used in the present invention typically can be preparedfrom dicarboxylic acids and diols which react in substantially equalproportions and are incorporated into the polyester polymer as theircorresponding residues. The polyesters of the present invention,therefore, can contain substantially equal molar proportions of acidresidues (100 mole %) and diol (and/or multifunctional hydroxylcompounds) residues (100 mole %) such that the total moles of repeatingunits is equal to 100 mole %. The mole percentages provided in thepresent disclosure, therefore, may be based on the total moles of acidresidues, the total moles of diol residues, or the total moles ofrepeating units. For example, a polyester containing 70 mole %terephthalic acid, based on the total acid residues, means the polyestercontains 70 mole % terephthalic acid residues out of a total of 100 mole% acid residues. Thus, there are 70 moles of terephthalic acid residuesamong every 100 moles of acid residues. In another example, a polyestercontaining 30 mole % 1,4-cyclohexanedimethanol residues, based on thetotal diol residues, means the polyester contains 30 mole %1,4-cyclohexanedimethanol residues out of a total of 100 mole % diolresidues. Thus, there are 30 moles of 1,4-cyclohexanedimethanol residuesamong every 100 moles of diol residues.

In one embodiment, the polyester or copolyesters comprise compositionswith a single diacid or combinations of diacids such as terephthalicacid or phthalic acid or other diacids with 8 to 20 carbon atoms, withcombinations of modifying glycols such as cyclohexanedimethanol orethylene glycol or other glycols with 2 to 20 carbon atoms.

In certain embodiments, the condensation polymer comprises at least onediol residue. In certain embodiments, the condensation polymer is apolyester comprising at least one dicarboxylic acid or an ester thereofand at least one diol, wherein the total of acid residues present is 100mole % and wherein the total of diol residues is 100 mole %. In certainembodiments, the condensation polymer, e.g., polyester, comprises1,4-cyclohexanedimethanol residues.

In certain embodiments, terephthalic acid, or an ester thereof, such as,for example, dimethyl terephthalate, or a mixture of terephthalic acidand an ester thereof, makes up most or all of the dicarboxylic acidcomponent used to form the polyesters useful in the invention. Incertain embodiments, terephthalic acid residues can make up a portion orall of the dicarboxylic acid component used to form the presentpolyester at a concentration of at least 70 mole %, such as at least 80mole %, at least 90 mole %, at least 95 mole %, at least 99 mole %, or100 mole %. In certain embodiments, polyesters with high amounts ofterephthalic acid can be used in order to produce higher impact strengthproperties. For purposes of this disclosure, the terms “terephthalicacid” and “dimethyl terephthalate” are used interchangeably herein. Inone embodiment, dimethyl terephthalate is part or all of thedicarboxylic acid component used to make the polyesters useful in thepresent invention. In all embodiments, ranges of from 70 to 100 mole %;or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100mole % terephthalic acid and/or dimethyl terephthalate and/or mixturesthereof may be used.

In addition to terephthalic acids and/or dimethyl terephthalateresidues, the dicarboxylic acid component of the polyesters useful inthe invention can comprise up to 50 mole %, up to 40 mole %, up to 30mole %, up to 20 mole %, up to 10 mole %, up to 5 mole %, or up to 1mole % of one or more modifying aromatic dicarboxylic acids. Yet anotherembodiment contains 0 mole % modifying aromatic dicarboxylic acids.Thus, if present, it is contemplated that the amount of one or moremodifying aromatic dicarboxylic acids can range from any of thesepreceding endpoint values including, for example, from 0.01 to 30 mole%, from 0.01 to 20 mole %, from 0.01 to 10 mole %, from 0.01 to 5 mole%, or from 0.01 to 1 mole % of one or more modifying aromaticdicarboxylic acids. In one embodiment, modifying aromatic dicarboxylicacids that may be used in the present invention include, but are notlimited to, those having up to 20 carbon atoms. Examples of modifyingaromatic dicarboxylic acids which may be used in this invention include,but are not limited to, isophthalic acid, 4,4-biphenyldicarboxylic acid,1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, andtrans-4,4-stilbenedicarboxylic acid, and esters thereof. In oneembodiment, isophthalic acid is the modifying aromatic dicarboxylicacid. In one embodiment, dimethyl isophthalate is used. In oneembodiment, dimethyl naphthalate is used.

The carboxylic acid component of the polyesters useful in the inventioncan be further modified with up to 10 mole %, such as up to 5 mole % orup to 1 mole % of one or more aliphatic dicarboxylic acids containing2-16 carbon atoms, such as, for example, malonic, succinic, glutaric,adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acidsor their corresponding esters including but not limited to dimethyladipate, dimethyl glutarate and dimethyl succinate. Certain embodimentscan also comprise 0.01 or more mole %, such as 0.1 or more mole %, 1 ormore mole %, 5 or more mole %, or 10 or more mole % of one or moremodifying aliphatic dicarboxylic acids. Yet another embodiment contains0 mole % modifying aliphatic dicarboxylic acids. Thus, if present, it iscontemplated that the amount of one or more modifying aliphaticdicarboxylic acids can range from any of these preceding endpoint valuesincluding, for example, from 0.01 to 10 mole % and from 0.1 to 10 mole%. The total mole % of the dicarboxylic acid component is 100 mole %.

In one embodiment, only esters of terephthalic acid and esters of theother modifying dicarboxylic acids may be used instead of thedicarboxylic acids. Suitable examples of dicarboxylic acid estersinclude, but are not limited to, the dimethyl, diethyl, dipropyl,diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the estersare chosen from at least one of the following: methyl, ethyl, propyl,and phenyl esters.

In one embodiment of the invention, the polyesters useful in theinvention can contain less than 30 mole % of one or more modifyingglycols. In another embodiment, the polyesters useful in the inventioncan contain 20 mole % or less of one or more modifying glycols. Inanother embodiment, the polyesters useful in the invention can contain10 mole % or less of one or more modifying glycols. In anotherembodiment, the polyesters useful in the invention can contain 5 mole %or less of one or more modifying glycols. In another embodiment, thepolyesters useful in the invention may contain 0 mole % modifyingglycols. Certain embodiments can also contain 0.01 or more mole %, suchas 0.1 or more mole %, 1 or more mole % of one or more modifyingglycols. Thus, if present, it is contemplated that the amount of one ormore modifying glycols can range from any of these preceding endpointvalues including, for example, from 0.01 to 15 mole % and from 0.1 to 10mole %.

Modifying glycols useful in the polyesters useful in the invention cancontain 2 to 16 carbon atoms. For TMCD-CHDM copolyesters (polymerscomprising 2,2,4,4-tetramethyl-1,3-cyclobutanediol,1,4-cyclohexanedimethanol, and terephthalic acid residues), a modifyingglycol can be residues of ethylene glycol. Examples of other suitablemodifying glycols useful in the polyesters described herein include, butare not limited glycols selected from ethylene glycol, diethyleneglycol, triethylene glycol, isosorbide, propane-1,3-diol,butane-1,4-diol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol),2,2,4,4,-tetramethyl-1,3-cyclobutanediol, pentane-1,5-diol,hexane-1,6-diol, 1,4-cyclohexanedimethanol, 3-methyl-pentanediol-(2,4),2-methylpentanediol-(1,4), 2,2,4-tri-methylpentane-diol-(1,3),2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3),hexanediol-(1,3), 1,4-di-(hydroxyethoxy)-benzene,2,2-bis-(4-hydroxycyclohexyl)-propane,2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane,2,2-bis-(3-hydroxyethoxyphenyl)-propane,2,2-bis-(4-hydroxypropoxyphenyl)-propane, and mixtures thereof.

In one TMCD copolyester embodiment, ethylene glycol is excluded as amodifying diol. For modified PETG and modified PCTG polymers, themodifying glycol can be a glycol other than ethylene glycol and1,4-cyclohexanedimethanol, for example.

Other modifying glycols can include polymeric diols (also known aspolyols) such as: Polyethylene glycol, polypropylene glycol, PTMG (alsocalled PTMEG or polyTHF), polyester polyol, polycarbonate polyol, andpolycaprolactone polyol. A polyol is an organic compound containingmultiple hydroxyl groups. A molecule with more than two hydroxyl groupsis a polyol, with three is a triol, one with with four is a tetrol andso on. By convention, polyols do not refer to compounds that containother functional groups. Polyols typically have weight average molecularweights (Mw) of about 500 to 5000 with Mw's of about around 1000 to 2000prefered. In embodiments, hydroxyl functionalities, meaning the numberof hydroxyl groups as polymer end groups, can range from about 1.9 toabout 2.1 for thermoplastic materials and from about 2.1 and higher forcrosslinked materials.

The polyesters useful in the polyester compositions and/or thepolyesterethers of the invention can comprise from 0 to 10 mole % of atleast one branching agent, for example, 0.01 to 5 mole % or 0.01 to 4mole % or from 0.01 to 3 mole % or from 0.01 to 2 mole % or from 0.01 toabout 1.5 mole % or from 0.01 to 1 mole % or from 0.1 to 5 mole % or 0.1to 4 mole % or from 0.1 to 3 mole % or from 0.1 to 2 mole % or from 0.1to about 1.5 mole % or from 0.1 to 1 mole or from 0.5 to 5 mole % or 0.5to 4 mole % or from 0.5 to 3 mole % or from 0.5 to 2 mole % or from 0.5to about 1.5 mole % or from 0.5 to 1 mole % or from 1 to 5 mole % or 1to 4 mole % or from 1 to 3 mole % or from 1 to 2 mole % or from 0.1 to0.7 mole %, or 0.1 to 0.5 mole %, based the total mole percentages ofeither the diol or diacid residues, based on at total of 100 mole %diols and 100 mole % diacids; respectively, of one or more residues of abranching monomer, also referred to herein as a branching agent, having3 or more carboxyl substituents, hydroxyl substituents, or a combinationthereof. In certain embodiments, the branching monomer or agent may beadded prior to and/or during and/or after the polymerization of thepolyester. The polyester(s) useful in the invention can thus be linearor branched.

Examples of branching monomers include, but are not limited to,multifunctional acids or multifunctional alcohols such as trimelliticacid, trimellitic anhydride, pyromellitic dianhydride,trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, citricacid, tartaric acid, 3-hydroxyglutaric acid, pentaerythritol, sorbitol,1,2,6-hexanetriol, glycerine tetra-maleaic anhydride, and trimesic acid,and the like or mixtures thereof.

In one embodiment, at least one of trimellitic acid, trimelliticanhydride, trimesic acid, pentaerythritol, glycerine, tetra-maleaicanhydride, and trimer acid can be used as the branching agent. Thebranching monomer may be added to the polyester reaction mixture orblended with the polyester in the form of a concentrate as described,for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176.

The polymers and/or polyesters useful in the invention can compriseresidues of 1,4-cyclohexanedimethanol in any amount, included but notlimited to at least one of the following amounts: from 0.01 to 100 mole%; from 0.01 to 100 mole %; from 0.01 to 99.99 mole %; from 0.10 to 99mole %; from 0.10 to 99 mole %; from 0.10 to 95 mole %; from 0.10 to 90mole %; from 0.10 to 85 mole %; from 0.10 to 80 mole %; from 0.10 to 70mole %; from 0.10 to 60 mole %; from 0.10 to 50 mole %; from 0.10 to 40mole %; from 0.10 to 35 mole %; from 0.10 to 30 mole %; from 0.10 to 25mole %; from 0.10 to 20 mole %; from 0.10 to 15 mole %; from 0.10 to 10mole %; from 0.10 to 5 mole %; from 1 to 100 mole %; from 1 to 99 mole%; 1 to 95 mole %; from 1 to 90 mole %; from 1 to 85 mole %; from 1 to80 mole %; from 1 to 70 mole %; from 1 to 60 mole %; from 1 to 50 mole%; from 1 to 40 mole %; from 1 to 35 mole %; from 1 to 30 mole %; from 1to 25 mole %; from 1 to 20 mole %; from 1 to 15 mole %; from 1 to 10mole %; from 1 to 5 mole %; 5 to 100 mole %; 5 to 99 mole %; 5 to 95mole %; from 5 to 90 mole %; from 5 to 85 mole %; from 5 to 80 mole %; 5to 70 mole %; from 5 to 60 mole %; from 5 to 50 mole %; from 5 to 40mole %; from 5 to 35 mole %; from 5 to 30 mole %; from 5 to 25 mole %;from 5 to 20 mole %; and from 5 to 15 mole %; from 5 to 10 mole %; from10 to 100 mole %; from 10 to 99 mole %; 10 to 95 mole %; from 10 to 90mole %; from 10 to 85 mole %; from 10 to 80 mole %; from 10 to 70 mole%; from 10 to 60 mole %; from 10 to 50 mole %; from 10 to 40 mole %;from 10 to 35 mole %; from 10 to 30 mole %; from 10 to 25 mole %; from10 to 20 mole %; from 10 to 15 mole %; from 20 to 100 mole %; from 20 to99 mole %; 20 to 95 mole %; from 20 to 90 mole %; from 20 to 85 mole %;from 20 to 80 mole %; from 20 to 70 mole %; from 20 to 60 mole %; from20 to 50 mole %; from 20 to 40 mole %; from 20 to 35 mole %; from 20 to30 mole %; and from 20 to 25 mole %; 30 to 100 mole %; from 30 to 99mole %; 30 to 95 mole %; from 30 to 90 mole %; from 30 to 85 mole %;from 30 to 80 mole %; from 30 to 70 mole %; from 30 to 60 mole %; from30 to 50 mole %; from 30 to 40 mole %; from 30 to 35 mole %; 40 to 100mole %; from 40 to 99 mole %; 40 to 95 mole %; from 40 to 90 mole %;from 40 to 85 mole %; from 40 to 80 mole %; from 40 to 70 mole %; from40 to 60 mole %; from 40 to 50 mole %; 50 to 100 mole %; from 50 to 99mole %; 50 to 95 mole %; from 50 to 90 mole %; from 50 to 85 mole %;from 50 to 80 mole %; from 50 to 70 mole %; from 50 to 60 mole %; 60 to100 mole %; from 60 to 99 mole %; 60 to 95 mole %; from 60 to 90 mole %;from 60 to 85 mole %; from 60 to 80 mole %; from 60 to 70 mole %; 70 to100 mole %; from 70 to 99 mole %; 70 to 95 mole %; from 70 to 90 mole %;from 70 to 85 mole %; from 70 to 80 mole %; from 60 to 70 mole %; 80 to100 mole %; from 80 to 99 mole %; 80 to 95 mole %; from 80 to 90 mole %;90 to 100 mole %; from 90 to 99 mole %; 90 to 95 mole %; 95 to 100 mole%; or from 95 to 99 mole %.

The polyesters may be prepared by any method known to one of ordinaryskill in the art.

The polymer composition useful in the invention can any of thetraditional compositions described as polyethylene terephthalate (PET),acid-modified polyethylene terephthalate (PETA), glycol modified PET(PETG), glycol modified poly(cyclohexylene dimethylene terephthalate)(PCTG), poly(cyclohexylene dimethylene terephthalate) (PCT), acidmodified poly(cyclohexylene dimethylene terephthalate) (PCTA), and anyof the foregoing polymers modified with2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD polyesters).

In one aspect, the polyester useful in the polymer compositions of theinvention comprises residues of isosorbide. In one embodiment, theisosorbide polymer can also comprise residues of ethylene glycol and/orcyclohexanedimethanol. In embodiments, the polyester comprises residuesof isosorbide and 1,4-cyclohexanedimethanol and optionally, ethyleneglycol. In embodiments, the polyester comprises residues of isosorbideand ethylene glycol and optionally, 1,4-cycloehexanedimethanol.

For terephthalate based polyesters, terephthalic acid can be present inan amount of from 70 to 100 mole %. Modifying dicarboxylic acids may bepresent in an amount of up to 30 mole %. In one embodiment, themodifying dicarboxylic acid can be isophthalic acid. Aliphatic diacidscan also be present in the terephthalic acid based polyesters of theinvention.

In certain embodiments, the polymer compositions of the invention caninclude copolyesters comprising residues of 70 to 100 mole %terephthalic acid, and optionally, 0.01 to 30 mole %, or 0.01 to 20 mole%, or 0.01 to 10 mole %, or 0.01 to 5 mole % of isophthalic acid, oresters there and/or mixtures thereof.

In certain embodiments, the polymer compositions of the invention caninclude copolyesters comprising 1,4-cyclohexanedimethanol and,optionally, ethylene glycol. In certain embodiments, the polymercompositions of the invention can include copolyesters comprising from50 mole % to 100 mole %, or from 60 mole % to 100 mole %, or from 65mole % to 100 mole %, or from 70 mole % to 100 mole %, or from 75 mole %to 100 mole %, or from 80 mole % to 100 mole %, or from 90 mole % fromto 100 mole %, or 95 mole % to 100 mole %, of residues of1,4-cyclohexanedimethanol and, optionally, from 0 mole % to 50 mole %,or from 0 mole % to 40 mole %, or from 0 mole % to 35 mole %, or from 0mole % to 30 mole %, or from 0 mole % to 25 mole %, or from 0 mole % to20 mole %, or from 0 mole % to 10 mole %, or from 0 mole % to 5 mole %,of residues of ethylene glycol.

In certain embodiments, the polymer compositions of the invention caninclude copolyesters comprising residues of 99 to 100 mole %terephthalic acid and residues of 99 to 100 mole %1,4-cyclohexanedimethanol. In certain embodiments, the polyestercomprises residues of diethylene glycol. In embodiments, the polyestercomprises residues of terephthalic acid, isophthalic acid and1,4-cyclohexanedimethanol. In embodiments, the polyester comprises from50 mole % to 99.99 mole % of residues of 1,4-cyclohexanedimethanol, 0.01mole % to 50 mole % of residues of ethylene glycol, and from 70 mole %to 100 mole % of residues of terephthalic acid. In embodiments, thepolyester comprises from 80 mole % to 99.99 mole % of residues of1,4-cyclohexanedimethanol and 0.01 mole % to 20 mole % of residues ofethylene glycol. In embodiments, the polyester comprises from 90 mole %to 99.99 mole % of residues of 1,4-cyclohexanedimethanol and 0.01 mole %to 10 mole % of residues of ethylene glycol. In embodiments, thepolyester comprises from 95 mole % to 99.99 mole % of residues of1,4-cyclohexanedimethanol and 0.01 mole % to 5 mole % of residues ofethylene glycol. In embodiments, the polyester comprises from 95 mole %to 99.99 mole % of residues of 1,4-cyclohexanedimethanol, 0.01 mole % to10 mole % of residues of ethylene glycol, from 90 mole % to 100 mole %of residues of terephthalic acid, and 0.01 to 10 mole % of residues ofisophthalic acid. In embodiments, the polyester comprises from 95 mole %to 100 mole % of residues of 1,4-cyclohexanedimethanol, 0.01 mole % to 5mole % of residues of ethylene glycol, from 95 mole % to 100 mole % ofresidues of terephthalic acid, and 0.01 to 5 mole % of residues ofisophthalic acid. In embodiments, the polyester consists essentially ofresidues of terephthalic acid or an ester thereof and1,4-cyclohexanedimethanol. In embodiments, the polyester comprisingconsist essentially of residues of terephthalic acid or an esterthereof, 1,4-cyclohexanedimethanol and ethylene glycol. In embodiments,the polyester comprises 0 mole % to 30 mole % or 0 mole % to 20 mole %or 0 mole % to 10 mole % or 0 mole % to 5 mole % or 0.01 mole % to 30mole % or 0.01 mole % to 20 mole % or 0.01 mole % to 10 mole % or 0.01mole % to 5 mole % isophthalic acid residues, based on a total of 100mole % acid residues and a total of 100 mole % of diol residues. Inembodiments, the polyester comprises from 20 mole % to less than 50 mole% of residues of 1,4-cyclohexanedimethanol, greater than 50 mole % to 80mole % of residues of ethylene glycol, and from 70 mole % to 100 mole %of residues of terephthalic acid. In embodiments, the polyestercomprises from 20 mole % to 40 mole % of residues of1,4-cyclohexanedimethanol, 60 mole % to 80 mole % of residues ofethylene glycol, and from 70 mole % to 100 mole % of residues ofterephthalic acid. In embodiments, the polyester comprises from 25 mole% to 40 mole % of residues of 1,4-cyclohexanedimethanol, 60 mole % to 75mole % of residues of ethylene glycol, and from 70 mole % to 100 mole %of residues of terephthalic acid. In embodiments, the polyestercomprises from 25 mole % to 35 mole % of residues of1,4-cyclohexanedimethanol, 65 mole % to 75 mole % of residues ofethylene glycol, and from 70 mole % to 100 mole % of residues ofterephthalic acid. In embodiments, the polyester comprises 0 to 20 mole% of residues of 1,4-cyclohexanedimethanol and 80 to 100 of residues ofethylene glycol.

In certain embodiments, the polyester comprises residues of neopentylglycol. In embodiments, the polyester comprises2,2,4,4-cyclobutanediol-1,3-cyclobutanediol residues.

In embodiments, the polyester comprises from 0.01 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and from 0.01 to 99mole % 1,4-cyclohexanedimethanol residues and 70 to 100 mole %terephthalic acid residues. In embodiments, the polyester comprises from20 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, from20 to 40 mole % 1,4-cyclohexanedimethanol residues, 20 to 60 mole % ofethylene glycol residues. In embodiments, the polyester comprises from0.01 to 15 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. Inembodiments, the polyester comprises from 15 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and from 60 to 85 mole% 1,4-cyclohexanedimethanol residues. In embodiments, the polyestercomprises from 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues and from 60 to 80 mole % 1,4-cyclohexanedimethanol residues. Inembodiments, the polyester comprises from 20 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and from 70 to 80 mole% 1,4-cyclohexanedimethanol residues and 70 to 100 mole % terephthalicacid residues. In embodiments, the polyester comprises from 30 to 40mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and from 60 to70 mole % 1,4-cyclohexanedimethanol residues and 70 to 100 mole %terephthalic acid residues.

In embodiments, the polyester component comprises residues of1,4-cyclohexanedicarboxylic acid or an ester thereof. In embodiments,the polyester component comprises residues ofdimethyl-1,4-cyclohexanedicarboxylate. In embodiments, the polyestercomponent comprises residues 1,4-cyclohexanedicarboxylic acid or anester thereof in the amount of from 70 to 100 mole % or from 80 to 100mole % or from 90 to 100 mole % or from 95 to 100 mole % or from 98 to100 mole %, based on a total of 100 mole % acid residues and a total of100 mole % diol residues.

In some aspects of the invention, the copolyesters useful in theinvention may comprise a diacid component comprising at least 70 mole %of residues of terephthalic acid, isophthalic acid, or mixtures thereof;and a diol component comprising (a) the residues of2,2,4,4-tetramethyl-1,3-cyclobutanediol and residues of1,4-cyclohexanedimethanol (TMCD Copolyesters).

In one embodiment, the polyester can comprise from 0.01 to 99.99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 99.99 to 0.01 mole% 1,4-cyclohexanedimethanol residues, or from 20 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 80 mole %1,4-cyclohexanedimethanol residues, or from 20 to less than 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and greater than 50 to80 mole % 1,4-cyclohexanedimethanol residues, or from 15 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 85 mole %1,4-cyclohexanedimethanol residues, or from 20 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 80 mole %1,4-cyclohexanedimethanol residues, or from 20 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 80 mole %1,4-cyclohexanedimethanol residues, or from 30 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 70 mole %1,4-cyclohexanedimethanol residues, or from 0.01 to 15 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 85 to 99.99 mole %1,4-cyclohexanedimethanol residues, or from 20 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, from 20 to 40 mole %1,4-cyclohexanedimethanol residues and 20 to 60 mole % of ethyleneglycol residues, and, for all of these ranges, optionally, 70 to 100mole % terephthalic acid or isophthalic residues or mixtures thereof,based on a total of 100 mole % acid residues and a total of 100 mole %diol residues.

In one embodiment, the polyester can comprise 20 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 80 mole %1,4-cyclohexanedimethanol residues and 70 to 100 mole % terephthalicacid residues, based on a total of 100 mole % acid residues and a totalof 100 mole % diol residues.

In certain embodiments, the polymer compositions of the invention maycan include copolyesters comprising, optionally, 0.01 to 30 mole %, or0.01 to 20 mole %, or 0.01 to 10 mole %, or 0.01 to 5 mole % ofterephalic acid and/or isophthalic acid, or esters there and/or mixturesthereof; and a diol component comprising: (a) from 20 to less than 50mole % of 1,4-cyclohexanedimethanol and residues from greater than 50 to80 mole % ethylene glycol residues; or from 20 to 40 mole % of1,4-cyclohexanedimethanol residues and from 60 to 80 mole % ethyleneglycol residues, or from 20 to 40 mole % of 1,4-cyclohexanedimethanolresidues and from 60 to 80 mole % ethylene glycol residues, or from 25to 40 mole % of 1,4-cyclohexanedimethanol residues and from 60 to 75mole % ethylene glycol residues, or from 25 to 35 mole % of1,4-cyclohexanedimethanol residues and from 65 to 75 mole % ethyleneglycol residues (PETG); or (b) from 50 mole % to 99.99 mole %, or from55 mole % to 99.99 mole %, or from 60 mole % to 99.99 mole %, or from 65mole % to 99.99 mole %, or from 70 mole % to 99.99 mole %, or from 75mole % to 99.99 mole %, or from 80 mole % to 99.99 mole %, or from 85mole % to 99.99 mole % percent, or from 90 mole % from to 99.99 mole %,or 95 mole % to 99.99 mole %, of residues of 1,4-cyclohexanedimethanoland from 0.01 mole % to 50 mole %, or from 0.01 mole % to 45 mole %, orfrom 0.01 mole % to 40 mole %, or from 0.01 mole % to 35 mole %, or from0.01 mole % to 30 mole %, or from 0.01 mole % to 25 mole %, or from 0.01mole % to 20 mole %, or from 0.01 mole % to 15 mole %, or from 0.01 mole% to 10 mole %, or from 0.01 mole % to 5 mole %, of residues of ethyleneglycol (PCTG); or (c) from 95 to 99.99 mole %, of residues of1,4-cyclohexanedimethanol and from 0.01 to 10 mole % or from 0.01 to 5mole % of residues of isophthalic acid, and from 0.01 to 10 mole % orfrom 0.01 to 5 mole % of residues of ethylene glycol (PCTA) or (d) 0 to20 mole % of residues of 1,4-cyclohexanedimethanol and 80 to 100 mole %of residues of ethylene glycol (PET or glycol modified PET) or (e)isosorbide polymers comprising 1,4-cyclohexanedimethanol and optionally,ethylene glycol or (f) isosorbide polymers comprising ethylene glycol or(g) (PCT as defined herein). In certain embodiments, the diol componentcan comprise from 10 mole % to 40 mole %, or from 15 mole % to 35 mole%, or from 20 mole % to 35 mole %, or from 20 mole % to 30 mole %, orfrom 20 mole % to 40 mole %, or from 20 mole % to 35 mole %, of residuesof isosorbide; from 30 mole % to 70 mole %, or from 40 mole % to 70 mole%, or from 45 mole % to 65 mole %, or from 45 mole % to 60 mole %, orfrom 45 mole % to 55 mole %, or from 47 mole % to 65 mole %, or from 48mole % from to 65 mole %, or 49 mole % to 65 mole %, or 50 mole % to 65mole %, or from 47 mole % to 60 mole %, or from 48 mole % from to 60mole %, or 49 mole % to 60 mole %, or 50 mole % to 60 mole %, ofresidues of 1,4-cyclohexanedimethanol and, optionally, from 0 mole % to40 mole %, or from 0 mole % to 35 mole %, or from 0 mole % to 30 mole %,or from 0 mole % to 25 mole %, or from 0 mole % to 20 mole %, or from 0mole % to 15 mole %, or from 0 mole % to 10 mole %, or from 0 mole % to5 mole %, of residues of ethylene glycol. In one embodiment, the diolcomponent can comprise from 18 mole % to 35 mole %, or from 20 mole % to35 mole %, of residues of isosorbide; from 40 mole % to 58 mole %, orfrom 45 mole % to 55 mole %, of residues of 1,4-cyclohexanedimethanol;and, from 15 mole % to 25 mole %, or from 20 mole % to 25 mole %, ofresidues of ethylene glycol.

In one embodiment, the polyesters useful in polymer compositions of theinvention can also comprise copolyester ethers (COPE), e.g., (PCCE)commercially available, for example, from Eastman Chemical Company. Theterm “polyesters” as used herein, is intended to includecopolyesterethers.

The COPE polymer has high melt strength, thus allowing articles to beblow molded from the molten polymer. Other desirable properties whichmake the COPE polymer especially useful in the manufacture of productssuch as medical supplies include its high level of clarity and low odor.Furthermore, the COPE polymer has a fast crystallization rate, allowingreasonably fast rates of production for molded articles such as bags,bottles or cast film.

The copolyesterethers according to this invention are derived from adicarboxylic acid component comprising and/or consisting essentially of1,4-cyclohexanedicarboxylic acid or an ester forming derivative thereofsuch as dimethyl-1,4-cyclohexanedicarboxylate. This acid and ester areboth sometimes referred to herein as DMCD. The diol component consistsessentially of 1,4-cyclohexanedimethanol (CHDM) and polytetramethyleneether glycol (PTMG). The copolyesterethers further can comprisebranching agents, for example, from about 0.1 to about 1.5 mole %, basedon the acid or glycol component, of a polyfunctional branching agenthaving at least 3 carboxyl or hydroxyl groups.

In embodiments, the dibasic acid component of the copolyesterethercomprises residues of 1,4-cyclohexanedicarboxylic acid ordimethyl-1,4-cyclohexanedicarboxylate having a trans isomer content ofat least 70% or at least 80% or at least 85%. In an embodiment, thedibasic acid component of the copolyesterether of this inventionconsists essentially of DMCD and can have a trans isomer content of atleast 70%, or at least 80% or at least 85%.

The polyesterether useful in the polymer compositions of the inventionwherein the polyester component comprises residues1,4-cyclohexanedicarboxylic acid or an ester thereof in the amount offrom 70-100 weight % or from 80 to 100 weight % or from 90 to 100 mole %or from 95 to 100 mole % or from 98 to 100 mole %, based on a total of100 mole % acid residues and a total of 100 mole % diol residues. Thepolyesterether can comprise residues of 1,4-cyclohexanedimethanol andpolytetramethylene ether glycol.

The polyesterether can comprise residues of from 15 mole % to 50 mole %or from 20 weight % to 50 weight % or from 25 to 50 weight % or from 30to 50 weight % or from 35 to 50 weight % or from 40 to 50 weight % orfrom 45 to 50 weight % or from 15 weight % to 45 weight % or from 20weight % to 45 weight % or from 25 to 45 weight % or from 30 to 45weight % or from 35 to 45 weight % or from 40 to 45 weight % or from 15weight % to 40 weight % or from 20 weight % to 40 weight % or from 25 to40 weight % or from 30 to 40 weight % or from 35 to 40 weight % or from15 weight % to 35 weight % or from 20 weight % to 35 weight % or from 25to 35 weight % or from 15 weight % to 30 weight % or from 20 weight % to30 weight % or from 25 to 30 weight % or from 15 weight % to 25 weight %of polytetramethylene ether glycol residues.

In one embodiment, the polyesterether can comprise residues of from 20weight % to 50 weight %, or from 25 weight % to 45 weight %, or from 30to 40 weight % of polytetramethylene ether glycol residues.

In one embodiment, the polyester portion of the polyesterether comprisesresidues of at least one glycol as described for the polyesters usefulin the invention. In certain embodiments, the polyester portion of thepolyesterether comprises residues of at least one glycol selected fromethylene glycol, diethylene glycol, triethylene glycol, isosorbide,propane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol(neopentyl glycol), 2,2,4,4,-tetramethyl-1,3-cyclobutanediol,pentane-1,5-diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol,3-methyl-pentanediol-(2,4), 2-methylpentanediol-(1,4),2,2,4-tri-methylpentane-diol-(1,3), 2-ethylhexanediol-(1,3),2,2-diethylpropane-diol-(1,3), hexanediol-(1,3),1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane,2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane,2,2-bis-(3-hydroxyethoxyphenyl)-propane,2,2-bis-(4-hydroxypropoxyphenyl)-propane, and mixtures thereof.

The polyesterether can comprise residues of from 15 weight % to 50weight %, or from 15 weight % to 45 weight %, or from 15 weight % to 40weight %, or from 15 weight % to 35 weight %, or from 15 weight % to 30weight %, or from 20 weight % to 50 weight %, or from 20 weight % to 45weight % of 1,4-cyclohexanedimethanol residues.

In one embodiment, useful copolyesterethers can have an inherentviscosity of from about 0.70 to about 1.5 dig as determined in 60/40(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at25° C. comprising

-   -   A. a dicarboxylic acid component comprising and/or consisting        essentially of 1,4-cyclohexanedicarboxylic acid, and    -   B. a glycol component consisting essentially of        -   (1) 1,4-cyclohexanedimethanol,        -   (2) from about 15 to about 50 weight percent, or from 20 to            35 weight percent, based on the weight of the            polyesterether, of polytetramethyleneether glycol having a            weight average molecular weight of about 500 to about 2000.

In one embodiment, useful copolyesterethers can have an inherentviscosity of from about 0.70 to about 1.5 dig as determined in 60/40(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at25° C. comprising

-   -   A. a dicarboxylic acid component comprising and/or consisting        essentially of 1,4-cyclohexanedicarboxylic acid,    -   B. a glycol component consisting essentially of        -   (1) 1,4-cyclohexanedimethanol,        -   (2) from about 15 to about 50 weight percent, or from 20 to            35 weight percent, based on the weight of the            polyesterether, of polytetramethyleneether glycol having a            weight average molecular weight of about 500 to about 2000,        -   (3) from about 0.1 to about 1.5 mole %, or 0.1 to 1.0 mole %            based on the total mole % of the acid or glycol component,            of a branching agent having at least three COOH or OH            functional groups and from 3 to 60 carbon atoms.

DMCD and CHDM are well known in the art and commercially available.“Man-Made Fibers: Science and Technology,” Vol. III, edited by Mark,Atlas and Cernia, published by Interscience Publishers describespreparation of DMCD and CHDM at page 85.

The PTMG component of the copolyesterethers useful in this invention iscommercially available, and is prepared by well known techniques. ThePTMG used in the copolyesterether of this invention has a molecularweight of between about 500 and about 1100, or about 1000. It is used inan amount of from about 15 to about 50%, or from about 20-35%, based onthe total weight of the copolyesterether. It is interesting to note thatif the molecular weight of the PTMG approaches 2000, the surface of filmproduced therefrom shows a white deposit.

The copolyesterether of this invention further can comprise the samemole percentages of residues of at least one branching agent asdescribed for the other polyesters useful in the invention. In oneembodiment, the branching agent can be present in an amount from about0.1 to about 1.5 mole %, based on the acid or glycol component, of apolybasic acid or polyhydric alcohol branching agent having at leastthree COOH or OH functional groups and from 3 to 60 carbon atoms. Estersof many such acids or polyols may also be used.

It should be understood that the total acid reactants for thepolyesterether useful in the invention should be 100 mole %, and thetotal glycol reactants should be 100 mole %. If the branching agent usedis a polybasic acid or anhydride, it will be calculated as part of the100 mole % acid. Likewise, if the branching agent is a polyol, it willbe calculated as part of the 100 mole % glycol. In some embodiments, thecomponents of the COPE are specified in weight percentages herein, basedon the total weight of the polyesterether equaling 100 weight %.

In other embodiments, the polyesterether may contain from about 0.1 toabout 1.5 mole %, or 0.1 to 1.0 mole %, based on the total mole % of theacid or glycol component, of a branching agent having at least threeCOOH or OH functional groups and from 3 to 60 carbon atoms as well.

In one embodiment, the copolyesterether has an I.V. of about 0.7 toabout 1.5 dL/g as determined in. 60/40 (wt/wt) phenol/tetrachloroethaneat a concentration of 0.5 g/100 ml at 25° C.

The polytetramethyleneether glycol component of the copolyesterether iscommercially available, and can be prepared by any technique known inthe art. In one embodiment, the polytetramethylene ether glycol can havea molecular weight of between about 500 to about 2000, or about 800 to2000, or about 500 to about 1200, or about 500 to about 1100, or about800 to about 1200.

The copolyesterether further can optionally comprise up to about 1.5mole % based on the acid or glycol component, of a polybasic orpolyhydric alcohol branching agent having at least three COOH or OHfunctional groups and from 3 to 60 carbon atoms. Esters of many suchacids or polyols may also be used. In one embodiment of the invention,the copolyesterethers of the invention do not include poly(aryleneethers). In another embodiment of the invention, blends of poly(aryleneethers) with other polymers are not included within the scope of theinvention.

In one embodiment, at least one branching agent useful in the COPE or inthe other polymers of the invention can be trimellitic acid ortrimellitic anhydride or combinations thereof. Although the acidreactant is said to “consist essentially of” 1,4-cyclohexanedicarboxylicacid, if the branching agent is a polybasic acid or anhydride, it willbe calculated as part of the 100 mole % acid. Likewise, the glycolcomponent is said to “consist essentially of: 1,4-cyclohexanedimethanoland polytetramethylene ether glycol, if the branching agent is a polyol,it will be calculated as part of the 100 mole % glycol.

In embodiments of the invention, the condensation polymer, polyester orpolyester portion of the polyesterether comprises residues of abranching agent. In embodiments, the polyester or the polyestercomponent of said polyesterether comprises 0.01 to 5 mole % or 0.01 to 4mole % or from 0.01 to 3 mole % or from 0.01 to 2 mole % or from 0.01 toabout 1.5 mole % or from 0.01 to 1 mole % or from 0.1 to 5 mole % or 0.1to 4 mole % or from 0.1 to 3 mole % or from 0.1 to 2 mole % or from 0.1to about 1.5 mole % or from 0.1 to 1 mole or from 0.5 to 5 mole % or 0.5to 4 mole % or from 0.5 to 3 mole % or from 0.5 to 2 mole % or from 0.5to about 1.5 mole % or from 0.5 to 1 mole % or from 1 to 5 mole % or 1to 4 mole % or from 1 to 3 mole % or from 1 to 2 mole % of at least onebranching agent or at least one polyfunctional branching agent, based ona total of 100 mole % acid residues and a total of 100 mole % diolresidues. In embodiments, the polyfunctional branching agent has atleast 3 carboxyl or hydroxyl groups. In embodiments, the polyfunctionalbranching agent comprises residues of trimellitic acid, trimelliticanhydride, trimesic acid, trimethyol ethane, trimethyolpropane,pentaerythritol, glycerine, tetra-maleaic anhydride, and trimer acid. Inembodiments, the polyfunctional branching agent comprises residues oftrimellitic anhydride, trimethyolpropane, pentaerythritol, glycerine,tetra-maleaic anhydride.

In other aspects of the invention, the Tg of the polyesters orcopolyesters useful in the invention can be, but is not limited to, atleast one of the following ranges: −10 to 130° C.; −10 to 125° C.; −10to 120° C.; −10 to 115° C.; −10 to 110° C.; −10 to 105° C.; −10 to 70°C.; −10 to 65° C.; −10 to 60° C.; −10 to 55° C.; −10 to 50° C.; −10 to45° C.; −10 to 40° C.; −10 to 35° C.; −10 to 30° C.; −10 to 25° C.;−10to 20° C.; −10 to 15° C.; −5 to 130° C.; −5 to 125° C.; −5 to 120° C.;−5 to 115° C.; −5 to 110° C.; −5 to 105° C.; −5 to 70° C.; −5 to 65° C.;−5 to 60° C.; −5 to 55° C.; −5 to 50° C.; −5 to 45° C.; −5 to 40° C.; −5to 35° C.; −5 to 30° C.; −5 to 25° C.; −5 to 20° C.; −5 to 15° C.; 60 to130° C.; 60 to 125° C.; 60 to 120° C.; 60 to 115° C.; 60 to 110° C.; 60to 105° C.; 60 to 100° C.; 60 to 95° C.; 65 to 130° C.; 65 to 125° C.;65 to 120° C.; 65 to 115° C.; 65 to 110° C.; 65 to 105° C.; 65 to 100°C.; 65 to 95° C.; 70 to 130° C.; 70 to 125° C.; 70 to 120° C.; 70 to115° C.; 70 to 110° C.; 70 to 105° C.; 75 to 130° C.; 75 to 125° C.; 75to 120° C.; 75 to 115° C.; 75 to 110° C.; 75 to 105° C.; 85 to 130° C.;85 to 125° C.; 85 to 120° C.; 85 to 115° C.; 85 to 110° C.; 85 to 105°C.; 85 to 100° C.; 85 to 95° C.; 80 to 130° C.; 80 to 125° C.; 80 to120° C.; 80 to 115° C.; 80 to 110° C.; 80 to 105° C.; 80 to 100° C.; 85to 130° C.; 85 to 125° C.; 85 to 120° C.; 85 to 115° C.; 85 to 110° C.;85 to 105° C.; 85 to 100° C.; 85 to 95° C.; 90 to 130° C.; 90 to 125°C.; 90 to 120° C.; 90 to 115° C.; 90 to 110° C.; 90 to 105° C.; 90 to100° C.; 95 to 130° C.; 95 to 125° C.; 95 to 120° C.; 95 to 115° C.; 95to 110° C.; 95 to 105° C.; 100 to 130° C.; 100 to 125° C.; 100 to 120°C.; 100 to 115° C.; 100 to 110° C.; 105 to 130° C.; 105 to 125° C.; 105to 120° C.; 105 to 115° C.; 110 to 130° C.; 110 to 125° C.; 110 to 120°C.; 115 to 130° C.; 115 to 125° C.; 115 to 120° C.; 115 to 130° C.; 115to 125° C.; 115 to 120° C.; and 120 to 130° C., as measured by ASTMMethod 3418.

For certain embodiments of the invention, the condensation polymers,e.g., polyesters, useful in the invention may exhibit at least one ofthe following inherent viscosities as determined in 60/40 (wt/wt)phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.:one of the following ranges: 0.35 to 1.5 dUg; 0.35 to 1.2 dUg; 0.35 to 1dUg; 0.50 to 1.5 dUg; 0.50 to 1.2 dUg; 0.50 to 1 dUg; 0.50 to 0.85 dUg;0.50 to 80 dUg; 0.50 to 0.75 dUg; 0.50 to less than 0.75 dUg; 0.50 to0.72 dUg; 0.50 to 0.70 dUg; 0.50 to less than 0.70 dUg; 0.50 to 0.68dUg; 0.50 to less than 0.68 dUg; 0.50 to 0.65 dUg; 0.55 to 1.5 dUg; 0.55to 1.2 dUg; 0.55 to 1 dUg; 0.55 to 0.85 dUg; 0.55 to 0.80 dUg; 0.55 to0.78 dUg; 0.55 to 0.75 dUg; 0.55 to less than 0.75 dUg; 0.55 to 0.72dUg; 0.55 to 0.70 dUg; 0.55 to less than 0.70 dUg; 0.55 to 0.68 dUg;0.55 to less than 0.68 dUg; 0.55 to 0.65 dUg; 0.60 to 1.5 dUg; 0.60 to1.2 dUg; 0.60 to 0.80 dUg; 0.60 to 0.75 dUg; 0.60 to 0.68 dUg; 0.70 to1.5 dUg 0.70 to 1.2 dUg; 0.80 to 1.5 dUg; and 0.80 to 1.2 dUg.

For certain embodiments of the invention, the polyesters useful in theinvention may exhibit at least one of the following inherent viscositiesas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C.: 0.70 to 1.2 dUg; 0.70 to 1.1dUg; 0.70 to 1 dUg; 0.70 to less than 1 dUg; 0.70 to 0.98 dUg; 0.70 to0.90 dUg; 0.70 to 0.85 dUg; 0.70 to 0.80 dUg; 0.70 to 1.2 dUg; 0.70 to1.1 dUg; 0.70 to 1 dUg; 0.70 to less than 1 dUg; 0.70 to 0.98 dUg; 0.70to 0.90 dUg; 0.70 to 0.85 dUg; 0.70 to 0.80 dL/g; 0.75 to 1.2 dUg; 0.75to 1.1 dUg; 0.75 to 1 dUg; 0.75 to 0.98 dUg; 0.75 to 0.90 dUg; 0.75 to0.85 dUg; 0.80 to 1.2 dUg; 0.80 to 1.1 dUg; 0.80 to 1 dUg; 0.80 to lessthan 1 dUg; 0.80 to 0.98 dUg; 0.80 to 0.90 dUg; 0.70 to 0.80 dL/g; 0.90to 1.2 dUg; 0.90 to 1.1 dUg; and 0.90 to 1 dUg.

It is contemplated that the polyester compositions of the invention canpossess at least one of the inherent viscosity ranges described hereinand at least one of the monomer ranges for the compositions describedherein unless otherwise stated. It is also contemplated that thepolyester compositions of the invention can possess at least one of theTg ranges described herein and at least one of the monomer ranges forthe compositions described herein unless otherwise stated. It is alsocontemplated that the polyester compositions of the invention canpossess at least one of the Tg ranges described herein, at least one ofthe inherent viscosity ranges described herein and at least one of themonomer ranges for the compositions described herein unless otherwisestated.

In one embodiment, the present invention can employ a primaryantioxidant of the hindered phenol type, a secondary antioxidant in thephosphite family and a chain extending agent with epoxidefunctionalities.

The primary antioxidants useful in this invention include a phenolicantioxidant.

Hindered phenols and hindered amines are the main types of primaryantioxidants used in thermoplastics.

Several characteristics can be considered in the choice of a hinderedphenolic antioxidant including the relative phenol content, whichaffects its reactivity, and the molecular weight sufficiently high toensure that the antioxidant does not migrate easily out of the polymer.

In one embodiment, the phenolic antioxidant can be sterically hinderedand/or relatively non-volatile. Examples of suitable phenolicantioxidants include hydroquinone, arylamine antioxidants such as4,4′-bis(α,α-dimethylbenzyl)diphenylamine, hindered phenol antioxidantssuch as 2,6-di-tert-butyl-4-methylphenol, butylated p-phenyl-phenol and2-(α-methylcyclohexyl)-4,6-dimethylphenol; bis-phenols such as2,2′-methylenebis-(6-tert-butyl-4-methylphenol),4,4′bis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),4,4′-butylene-bis(6-tert-butyl-3-methylphenol),methylenebis(2,6di-tertbutylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol), and2,2′-thiobis(4-methyl-6-tert-butylphenol); tris-phenols such as1,3,5-tris(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)-hexahydro-s-triazine,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene andtri(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite; and pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] the last of whichis commercially available as Irganox™ 1010 antioxidant.

In a further aspect, the antioxidant is a primary antioxidant, asecondary antioxidant, or combinations thereof. In a still furtheraspect, the primary antioxidant is selected from at least one hinderedphenol, at least one secondary aryl amine, or a combination thereof.

In a further aspect, the at least one hindered phenol useful in thepolymer compositions of the invention comprises one or more compoundsselected from triethylene glycolbis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],1,6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine,pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],2,2-thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate],octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, benzenepropanoicacid3,5-bis(1,1-dimethylethyl)-4-hydroxy-2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediylester, N,N′-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), tetrakis(methylene3,5-di-tert-butyl-hydroxycinnamate)methane,4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)phenol(Irganox®565), and octadecyl 3,5-di-tert-butylhydroxyhydrocinnamate.

In one embodiment, the phenolic antioxidants useful in the polymercompositions of the invention can beoctadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate (CAS number2082-79-3; pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (CAS #6683-198,otherwise known as Irganox™ 1010);N,N′-hexane-1,6-diyl-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl]propionamide](CAS #23128-747-, Irganox™ 1098); benzenepropanoic acid3,5-bis(1,1-dimethylethyl)-4-hydroxyoctadecyl ester (Irganox™1076). TheIrganox phenolic brand of additives can be commercially obtained fromBASF). In a further aspect, the hindered phenol comprisesoctadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate. In an evenfurther aspect, at least one hindered phenol is3,5-bis(1,1-dimethylethyl)-4-hydroxy-2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediylester.

In one embodiment, the phenolic antioxidant is present in the amount offrom 0.01 to 5 weight %, or from 0.01 weight % to 4 weight %, or from0.01 weight % to 3 weight %, or from 0.01 weight % to 2.0 weight %, orfrom 0.01 weight % to 1.0 weight %, or from 0.01 weight % to 0.90 weight%, or from 0.01 weight % to 0.80 weight %, or from 0.01 weight % to 0.75weight %, or from 0.01 to 0.70 weight %, or from 0.01 to 0.60 weight %,or from 0.01 weight % to 0.50 weight % or from 0.10 weight % to 5 weight%, or from 0.10 weight % to 4 weight %, or from 0.10 weight % to 3weight %, or from 0.10 weight % to 2.0 weight %, or from 0.10 weight %to 1.0 weight %, or from 0.10 weight % to 0.90 weight %, or from 0.10weight % to 0.80 weight %, or from 0.10 weight % to 0.75 weight %, orfrom 0.10 weight % to 0.70 weight %, or from 0.10 weight % to 0.60weight %, or from 0.10 weight % to 0.50 weight %, or from 0.25 weight %to 5 weight %, or from 0.25 weight % to 4 weight %, or from 0.25 weight% to 3 weight %, or from 0.25 weight % to 2.0 weight %, or from 0.25weight % to 1.0 weight %, or from 0.25 weight % to 0.90 weight %, orfrom 0.25 weight % to 0.80 weight %, or from 0.25 weight % to 0.75weight %, or from 0.25 weight % to 0.70 weight %, or from 0.25 weight %to 0.60 weight %, or from 0.25 weight % to 0.50 weight %, or from 0.50weight % to 5 weight %, or from 0.50 weight % to 4 weight %, or from0.50 weight % to 3 weight %, or from 0.50 weight % to 2.0 weight %, orfrom 0.50 weight % to 1.5 weight %, or from 0.50 weight % to 1.0 weight%, or from 0.50 weight % to 0.90 weight %, or from 0.50 weight % to 0.80weight %, or from 0.50 weight % to 0.75 weight %, or from 0.80 weight %to 1.2 weight %, based on the total weight of the polymer compositionequaling 100 weight %.

In certain aspects of the invention, the primary antioxidant can bepresent (total loading) in the polymer compositions of the invention inthe amount of from 0.01 weight % to 5 weight % or from 0.01 weight % to4 weight % or from 0.01 weight to 3 weight % or from 0.01 to 2.0 weight% or from 0.01 to 1.5 or from 0.01 to 1 weight % or from 0.01 to 0.75weight % or from 0.01 to 0.50 weight % or from or from 0.10 weight % to5 weight % or from 0.10 weight % to 4 weight % or from 0.10 weight to 3weight % or from 0.10 to 2.0 weight % or from 0.10 to 1.5 or from 0.10to 1 weight % or from 0.10 to 0.75 weight % or from 0.10 to 0.60 weight% or from, based on the total weight of the polymer composition equaling100 weight %.

In certain aspects of the invention, the primary antioxidant can bepresent (total loading) in the polymer compositions of the invention inthe amount of from 0.01 to 2.0 weight %, or from 0.10 to 2.0 weight %,from 0.01 to 1.0 weight %, or from 0.10 to 1.0 weight %, or from 0.10 to1.5, or from 0.50 to 1.5, or from 0.75 to 1.25, or from 0.10 to 60weight %, based on the total weight of the polymer composition equaling100 weight %.

In one aspect of the invention, the primary antioxidant can be present(total loading) in the polymer compositions of the invention in theamount of from 0.01 to 1.0 weight %, 0.01 to 0.90 weight % or from 0.10to 1.0 weight %, 0.10 to 0.90 weight % from 0.20 to 1.0 weight %, 0.20to 0.90 weight % from 0.25 to 1.0 weight % or 0.25 to 0.90 weight %,based on the total weight of the polymer composition.

A secondary antioxidant is useful in the present invention. Molecularweight, reactivity and hydrolytic stability can be considered in thechoice of secondary antioxidant. Some examples of secondary antioxidantsare thiodipropionates, phosphites and metal salts. Thiopropionates aremostly used in polyolefins.

Phosphites are secondary antioxidants useful in one embodiment of thisinvention.

The secondary antioxidant can be selected from an organophosphate orthioester, or a combination thereof. In a still further aspect, thesecondary anti-oxidant comprises one or more compounds selected fromtris(nonyl phenyl)phosphite [Weston™399, available from Addivant,Conn.), tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4′-diylbisphosphonite,tris(2,4-di-tert-butylphenyl)phosphite (Irgafos™168, available fromBASF), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-dicumylphenyl)pentaerythritoldiphosphite, and distearylpentaerythritol diphosphite.

In one embodiment, the polymer composition of the invention contains atleast one phosphite comprising an aryl phosphite or an arylmonophosphite. As used herein, the term “aryl monophosphite” refers to aphosphite stabilizer which contains: (1) one phosphorus atom permolecule; and (2) at least one aryloxide (which may also be referred toas a phenoxide) radical which is bonded to the phosphorus. In oneembodiment, the aryl monophosphite contains C₁ to C₂₀, or C₁ to C₁₀, orC₂-C₆ alkyl substituents on at least one of the aryloxide groups.Example of C₁ to C₂₀ alkyl substituents include but are not limited tomethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and iso-butyl,tertiary butyl, pentyl, hexyl, octyl, nonyl, and decyl. Preferred arylgroups include but are not limited to phenyl and naphthyl.

In one embodiment, the phosphites useful in the invention comprisetertiary butyl substituted aryl phosphites. In another embodiment, thearyl monophosphite comprises at least one of triphenyl phosphite, phenyldialkyl phosphites, alkyl diphenyl phosphites,tri(nonylphenyl)phosphite, tris-(2,4-di-t-butylphenyl)phosphite,bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, (believed to beIrgafos™38, available from BASF),2,2,2-nitrilo[triethyltris(3,3,5,5-tetra-tert-butyl-1,1-biphenyl-diyl)phosphite(believed to be Irgafos™12, available from BASF. In another embodiment,the aryl monophosphite is selected from one or more oftris-(2,4-di-t-butylphenyl)phosphite,bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, and2,2,2-nitrilo[triethyltris(3,3,5,5-tetra-tert-butyl-1,1-biphenyl-diyl)phosphite.In a further embodiment, an aryl monophosphite useful in the inventionis tris-(2,4-di-t-butylphenyl)phosphite.

In one embodiment, suitable secondary antioxidant additives include, forexample, organic phosphites such as, tris(nonyl phenyl)phosphite,tris(2,4-di-t-butylphenyl)phosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite or the like; or combinations comprising atleast one of the foregoing antioxidants.

In one aspect, the secondary antioxidant is present in an amount fromabout 0.01 weight % to about 3.0 weight %, or from 0.01 weight % to 2weight %, or from 0.01 weight % to 1 weight % or from 0.10 weight % to 5weight %, or from 0.10 weight % to 4 weight %, or from 0.10 weight % to3 weight %, or from 0.10 weight % to 2 weight %, or from 0.10 weight %to 1 weight %, or from 0.25 weight % to 1 weight %, or from 0.25 weight% to 0.75 weight %, based on the total weight of the polymercomposition.

In a further aspect, the secondary antioxidant is present in an amountfrom about 0.01 weight % to about 2.5 weight %. In still another aspect,the secondary antioxidant is present in an amount from about 0.5 weight% to about 2.5 weight %. In yet another aspect, the secondaryantioxidant is present in an amount from about 0.5 weight % to about 2.0weight % In still another aspect, the secondary antioxidant is presentin an amount from about 0.05 weight % to about 0.75 weight %. In stillanother aspect, the secondary antioxidant is present in an amount fromabout 0.05 weight % to about 0.75 weight %. In certain embodiments, thesecondary antioxidant is present in an amount from about 0.1 weight % toabout 1.0 weight %, or about 0.2 weight % to about 0.8 weight %, or 0.25to 0.75 weight %. In one embodiment, the secondary antioxidant ispresent in an amount from about 0.35 weight % to about 0.65 weight %.

In certain aspects of the invention, the weight ratio of primaryantioxidant to secondary antioxidant present in the polymer compositionsuseful in the invention can be from 5:1 to 1:5. In certain aspects ofthe invention, the weight ratio of primary antioxidant to secondaryantioxidant can be 5:1 or 4:1 or 3:1 or 2:1 or 1:1 or 1:2 or 1:3 or 1:4or 1:5. In certain aspects of the invention, the weight ratio of primaryto secondary antioxidant is 1:1 or 1:2 or 1:3 or 1:4 or 1:5. In certainaspects of the invention, the weight ratio of primary antioxidant tosecondary antioxidant is 2:1 to 1:2, e.g., 2:1. In certain aspects ofthe invention, the weight ratio of primary antioxidant to secondaryantioxidant is in the range from 1.1:1 to 4:1, or 1.2:1 to 4:1, or 1.5:1to 4:1, or 1.6:1 to 4:1, or 1.8:1 to 4:1, or 2:1 to 4:1, or 1.1:1 to3:1, or 1.2:1 to 3:1, or 1.5:1 to 3:1, or 1.6:1 to 3:1, or 1.8:1 to 3:1,or 2:1 to 3:1, 1.1:1 to 2.5:1, or 1.2:1 to 2.5:1, or 1.5:1 to 2.5:1, or1.6:1 to 2.5:1, or 1.8:1 to 2.5:1, or 2:1 to 2.5:1.

The polymers of the invention can comprise at least one chain extendingagent. Suitable chain extending agents include, but are not limited to,multifunctional (including, but not limited to, bifunctional)isocyanates, multifunctional epoxides, including for example, andphenoxy resins. In one embodiment, the chain extending agents haveepoxide dependent groups. In one embodiment, the chain extendingadditive can be one or more styrene-acrylate copolymers with epoxidefunctionalities. In one embodiment, the chain extending additive can beone or more copolymers of glycidyl methacrylate with styrene.

In certain embodiments, chain extending agents may be added at the endof the polymerization process or after the polymerization process. Ifadded after the polymerization process, chain extending agents can beincorporated by compounding or by addition during conversion processessuch as injection molding or extrusion. The amount of chain extendingagent used can vary depending on the specific monomer composition usedand the physical properties desired but is generally about 0.1 percentby weight to about 10 percent by weight, or from about 0.1 to about 5percent by weight, based on the total weight of the polymer.

Chain extending additives can also be added during melt processing tobuild molecular weight through ‘reactive extrusion’ or ‘reactive chaincoupling or any other process known in the art.

Chain extending agents useful in the invention can include, but are notlimited to, copolymers of glycidyl methacrylate (GMA) with alkenes,copolymers of GMA with alkenes and acrylic esters, copolymers of GMAwith alkenes and vinyl acetate, copolymers of GMA and styrene. Suitablealkenes comprise ethylene, propylene, and mixtures of two or more of theforegoing. Suitable acrylic esters comprise alkyl acrylate monomers,including, but not limited to, methyl acrylate, ethyl acrylate, propylacrylate, butyl acrylate, and combinations of the foregoing alkylacrylate monomers. When present, the acrylic ester can be used in anamount of 15 weight % to 35 weight %, based on the total amount ofmonomer used in the copolymer, or in any other range described herein.When present, vinyl acetate can be used in an amount of 4 weight % to 10weight % based on the total amount of monomer used in the copolymer.

In certain embodiments, the chain extender comprises acrylic esterscomprising monomers selected from alkyl acrylate monomers, including,but not limited to, methyl acrylate, ethyl acrylate, propyl acrylate,butyl acrylate, and combinations thereof. In embodiments, the chainextender is a copolymer comprising at least one acrylic ester andstyrene.

Illustrative examples of suitable chain extending agents compriseethylene-glycidyl acrylate copolymers, ethylene-glycidyl methacrylatecopolymers, ethylene-glycidyl methacrylate-vinyl acetate copolymers,ethylene-glycidyl methacrylate-alkyl acrylate copolymers,ethylene-glycidyl methacrylate-methyl acrylate copolymers,ethylene-glycidyl methacrylate-ethyl acrylate copolymers, andethylene-glycidyl methacrylate-butyl acrylate copolymers.

Examples of useful chain extending agents include but are not limited toJoncryl 4368, Joncryl™4468 (copolymers of glycidyl methacrylate withstyrene), Joncryl™4368, Joncryl™4470, Joncryl™4370, Joncryl™ 4400,Joncryl™4300, Joncryl™4480, Joncryl™4380, Joncryl™4485, Joncryl™4385,and mixtures thereof commercially available from BASF Corporation, NewJersey.

In one embodiment, the chain extending agents can be styrene-acrylatecopolymers with glycidyl groups. In another embodiment, the chainextending agent can be a copolymer of glycidyl methacrylate and styrene.

In one embodiment, the polymeric chain extending agent can have anaverage of greater than or equal to 2 pendant epoxy groups per molecule,greater than or equal to 3 pendant epoxy groups per molecule; or anaverage of greater than or equal to 4 pendant epoxy groups per molecule;or an average of greater than or equal to 5 pendant epoxy groups permolecule; or an average of greater than or equal to 6 pendant epoxygroups per molecule; or an average of greater than or equal to 7 pendantepoxy groups per molecule; or more specifically, an average of greaterthan or equal to 8 pendant epoxy groups per molecule, or, morespecifically, an average of greater than or equal to 11 pendant epoxygroups per molecule, or, more specifically, an average of greater thanor equal to 15 pendant epoxy groups per molecule, or, more specifically,an average of greater than or equal to 17 pendant epoxy groups permolecule. The lower limits of the number of pendant epoxy groups may bedetermined by one of ordinary skill in the art to apply to specificmanufacturing conditions and/or to particular end-use applications. Incertain embodiments, the chain extending agent can have from 2 to 20pendant epoxy groups per molecule, or from 5 to 20 pendant epoxy groupsper molecule, or from 2 to 15 pendant epoxy groups per molecule, or from2 to 10 pendant epoxy groups per molecule, or from 2 to 8 pendant epoxygroups per molecule, or 3 to 20 pendant epoxy groups per molecule, orfrom 3 to 15 pendant epoxy groups per molecule, or from 5 to 15 pendantepoxy groups per molecule, or from 3 to 10 pendant epoxy groups permolecule, or from 5 to 10 pendant epoxy groups per molecule, or from 3to 8 pendant groups per molecule, or from 3 to 7 pendant epoxy groupsper molecule.

The composition comprises 0.1 weight % to 20 weight % of polymeric chainextending agent, based on the total weight of the composition. Withinthis range, the composition can comprise less than or equal to 15 weight%, or, more specifically less than or equal to 10 weight %, or, evenmore specifically, less than or equal to 8 weight % chain extendingagent. Also within this range, the composition may comprise greater thanor equal to 0.5 weight %, or greater than or equal to 1 weight %, orgreater than or equal to 4 weight % chain extending agent, based on thetotal weight of the polymer composition equaling 100 weight %.

In certain aspects of the invention, the chain extending agent can bepresent (total loading) in the polymer composition of the invention inthe amount of from 0.01 weight % to 5 weight %, or from 0.01 weight % to4 weight %, or from 0.01 weight % to 3 weight %, or from 0.01 weight %to 2, weight % or from 0.01 weight % to 1 weight %, or from 0.10 weight% to 5 weight %, or from 0.10 weight % to 4 weight %, or from 0.10weight % to 3 weight %, or from 0.10 weight % to 2 weight %, or from0.10 weight to 1.5 weight %, or from 0.10 weight % to 1 weight, or from0.25 weight % to 5 weight %, or from 0.25 weight % to 4 weight %, orfrom 0.25 weight % to 3 weight %, or from 0.25 weight % to 2 weight %,or from 0.25 weight to 1.5 weight %, or from 0.25 weight % to 1 weight,or from 0.25 weight % to 0.75 weight %, or from 0.50 weight % to 5weight %, or from 0.50 weight % to 4 weight %, or from 0.50 weight % to3 weight %, or from 0.50 weight % to 2 weight %, or from 0.50 weight to1.5 weight %, or from 0.50 weight to 1.2 weight %, or from 0.50 weight %to 1 weight, based on the total weight of the polymer compositionequaling 100 weight %. In certain embodiments, the chain extending agentcan be present (total loading) in the polymer composition of theinvention in the amount of from 0.25 weight % to 0.75 weight %, or from0.30 weight % to 0.70 weight %, or from 0.4 weight % to 0.6 weight %.

In certain aspects of the invention, the chain extending agent ispresent (total loading) in the polymer composition of the invention inthe amount of from 0.01 weight % to 1 weight % or from 0.10 weight % to1 weight % or from based on the total weight of the polymer composition.

The initial amount of the chain extending agent used and order ofaddition will depend upon the specific chain extending agent chosen andthe specific amounts of polyester employed.

In one embodiment, the weight ratio of chain extending agent to primaryantioxidant present in the polymer compositions useful in the inventioncan be from 5:1 to 1:5. In certain aspects of the invention, the weightratio of chain extending agent to primary antioxidant can be 5:1 or 4:1or 3:1 or 2:1 or 1:1 or 1:2 or 1:3 or 1:4 or 1:5. In certain aspects ofthe invention, the weight ratio of chain extending agent to primaryantioxidant is 3:1 to 1:2, or 2.5-3:1. In certain aspects of theinvention, the weight ratio of chain extending agent to primaryantioxidant is 1:2 or 3:1.

In certain aspects of the invention, the weight ratio of chain extendingagent to secondary antioxidant present in the polymer compositionsuseful in the invention can be from 5:1 to 1:5. In certain aspects ofthe invention, the weight ratio of chain extending agent to secondaryantioxidant can be 5:1 or 4:1 or 3:1 or 2:1 or 1:1 or 1:2 or 1:3 or 1:4or 1:5. In certain aspects of the invention, the weight ratio of chainextending agent to secondary antioxidant is 3:1. In certain aspects ofthe invention, the weight ratio of chain extending agent to secondaryantioxidant is 1:1 or 1.5:1 or 1.3:1. In another embodiment, the weightratio of chain extending agent to secondary antioxidant is 1:1 to 3:1,or 1:1 to 2:1.

In certain embodiemnts, the polymer composition comprises: (1) at leastone hindered phenolic antioxidant that comprises one or more compoundsselected from pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,octadecyl-3-(3,5-d i-t-butyl-4-hyd roxyphenyl)-propionate,N,N′-hexane-1,6-diyl-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionamide,benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxyoctadecylester, and octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate(CAS number 2082); (2) at least one phosphite that is chosen fromtris-(2,4-di-t-butylphenyl)phosphite,bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, or2,2,2-nitrilo[triethyltris(3,3,5,5-tetra-tert-butyl-1,1-biphenyl-diyl)phosphite;and (3) at least one chain extending agent that is a copolymer ofglycidyl methacrylate and styrene.

In certain embodiments, the polymer composition comprises at least onehindered phenolic antioxidant that is pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; at least onephosphite that is tris(2,4-di-tert-butylphenyl)phosphite; and at leastone chain extending agent that is Joncryl™4468 additive.

In one embodiment of the present invention, a primary antioxidant isincorporated in the hindered phenol family, i.e., Irganox™ 1010commercially available from BASF Corporation, New Jersey, in the amountsof 0.01 to about 2.0% by weight, a secondary antioxidant in thephosphite family, i.e, Irgafos™168 commercially available from BASFCorporation, New Jersey, in the amounts of 0.01 to 2.0% by weight, and achain extending agent in the styrene-acrylate copolymer family, i.e.,Joncryl™4468 commercially available from BASF Corporation, New Jersey,in the amounts from 0.01 to 2.0% by weight into a polyester orcopolyester.

In one embodiment, the polymer composition comprises (1) at least onephenolic antioxidant in the amount of from 0.01 weight % to 2.0 weight%, (2) at least one phosphite in the amount of from 0.10 weight % to 1.0weight %, and (3) said chain extending agent in the amount of from 0.25weight % to 2.0 weight percent, based on the total weight of the polymercomposition.

In one embodiment, the polymer composition comprises (1) at least onephenolic antioxidant in the amount of from 0.10 weight % to 1.5 weight%, or from 0.10 weight % to 1.0 weight %, or from 0.50 weight % to 1.5weight %, or from 0.75 weight % to 1.25 weight %, (2) at least onephosphite in the amount of from 0.10 weight % to 1.0 weight %, or 0.10weight % to 0.75 weight %, or from 0.25 weight % to 0.75 weight %, and(3) at least one chain extending agent in the amount of from 0.10 weight% to 1.0 weight %, or 0.25 weight % to 1.0 weight, or from 0.25 weight %to 0.75 weight %.

In one embodiment, the polymer composition comprises (1) at least onephenolic antioxidant in the amount of from 0.75 weight % to 1.25 weight%, (2) at least one phosphite in the amount of 0.10 weight % to 1.0weight %, or from 0.25 weight % to 0.75 weight %, and (3) at least onechain extending agent in the amount of 0.10 weight % to 1.0 weight %, orfrom 0.25 weight % to 0.75 weight %.

The weight percentages specified herein can also be combined with theratios of additives to each other that are specified. They can also becombined with the particular classifications of additives that aredescribed herein. The weight ratios of one additive to another or weightpercentages of additives are calculated based on the weight of theadditive compared to the total weight of the polymer composition at thetime of loading the additive into the composition (total loading)wherein all components equal 100 weight %.

In one embodiment, the stabilizer compositions useful in the inventioncan improve or maintain color, reduce the loss of number averagemolecular weight, and/or inherent viscosity, and/or reduce the totalnumber of carboxyl end groups, under the conditions as specified herein.

These combinations of primary antioxidant, secondary antioxidant, andchain extending agent useful in the present invention have been shownherein to be effective in certain polymers, for example polycondensationpolymers, e.g. polyester and copolyester classes of polymers. Theimproved thermal oxidative and hydrolytic stability can be measured byany method known in the art, for example, through using gel-permeationchromatography and through visual color observations, colorimeter,and/or spectrophotometry. Viscosity improvements can be measured by anymethod known in the art, for example, using parallel plate rheometry orinherent viscosity measures.

Numbers of carboxyl end groups can be measured by titration.

To make stabilized compositions, blends of these antioxidants, chainextending agent and polyesters and copolyesters can either be prepareddirectly during the polymerization process or compounded to producepellets using typical plastics compounding and extrusion techniques.These fully compounded or prepared pellets can be processed usingconvention polymer processing methods, or concentrates of the aboveadditives can be prepared and diluted with neat polyesters andcopolyesters, to make sheet, film, injection molded articles, and blowmolded articles, using conventional thermoplastic processing methods. Tomake stabilized compositions, blends of these antioxidants, chainextending agent and polyesters and copolyesters can either be prepareddirectly during the polymerization process or compounded to producepellets using typical plastics compounding and extrusion techniques. Tomake powders that are useful for 3D printing applications or powdercoating of metals, the compounded pellets can be subsequently ground andreduced in size at cryogenic temperatures.

In addition, the polymer compositions useful in this invention may alsocontain at least one other additive selected from colorants, dyes, moldrelease agents, flame retardants, plasticizers, nucleating agents, otherstabilizers (including but not limited to, UV stabilizers, thermalstabilizers, hydrolytic stabilizers), fillers, and impact modifiers. Inembodiments, the polymer compositions can contain from 0.01 to 25% byweight or 0.01 to 20% by weight or 0.01 to 15% by weight or 0.01 to 10%by weight or 0.01 to 5% by weight of the total weight of the polymercomposition of common additives such as colorants, dyes, mold releaseagents, flame retardants, plasticizers, nucleating agents, stabilizers,including but not limited to, UV stabilizers, thermal stabilizers and/orreaction products thereof, fillers, and impact modifiers. Examples oftypical commercially available impact modifiers well known in the artand useful in this invention include, but are not limited to,ethylene/propylene terpolymers; functionalized polyolefins, such asthose containing methyl acrylate and/or glycidyl methacrylate;styrene-based block copolymer impact modifiers and various acryliccore/shell type impact modifiers. For example, UV additives can beincorporated into articles of manufacture through addition to the bulk,through application of a hard coat, or through coextrusion of a caplayer. Residues of such additives are also contemplated as part of thepolymer composition.

Reinforcing materials may be useful in the polymer compositions of thisinvention. The reinforcing materials may include, but are not limitedto, carbon filaments, silicates, mica, clay, talc, titanium dioxide,Wollastonite, glass flakes, glass beads and fibers, and polymeric fibersand combinations thereof. In one embodiment, the reinforcing materialsare glass, such as, fibrous glass filaments, mixtures of glass and talc,glass and mica, and glass and polymeric fibers.

In certain embodiments, the polymer useful in the polymer compositionsof this invention can be blended with any other polymer known in theart. For example, the polymer compositions of the invention can compriseat least one polymer chosen from at least one of the following:poly(etherimides), polyphenylene oxides, poly(phenyleneoxide)/polystyrene blends, polystyrene resins, polyphenylene sulfides,polyphenylene sulf ide/sulf ones, poly(ester-carbonates),polycarbonates, polysulfones, polysulf one ethers, andpoly(ether-ketones).

In some embodiments of the invention, the polymer compositions of theinvention and/or the polymer blends of the invention exclude: (1)polycarbonate; (2) bisphenol A polycarbonates; (3) blends ofpolycarbonate and poly(butylene) terephthalate (PBT); (4) poly(butylene)terephthalate or polyesters containing butanediol; (5) terephthalatebased polyesters containing butanediol and bisphenol A polycarbonates;(6) poly(arylene) ethers; (7) cellulose esters; (8) polypropylene; (9)PET homopolymer; (10) carbon nanotubes; and/or (11) polyphosphates.

In one embodiment, certain additional polymers other than the onesdescribed in the polymer compositions of the invention, e.g.,polycarbonate, can be present in an amount of 50 weight % or less, or 40weight % or less, or 30 weight % or less, or 20 weight % or less, or 10weight % or less, or 5 weight % or less; in another embodiment, 0.01 to50 weight %, or 1 to 50 weight %, or 5 to 50 weight %, or 0.01 to 40weight %, or 0.01 to 30 weight % or 0.01 to 20 weight %, or 0.01 to 10weight % or 0.01 to 5 weight %.

In certain embodiments, the polymer compositions of the invention cancomprise a polymer blend of at least one polymer described herein and atleast one other polymer. In embodiments, the polymer blend comprises atleast one condensation polymer and the stabilizer composition (asdescribed herein) and at least one other polymer selected from liquidcrystalline polyesters/amides/imides, polyesteramides, polyimides,polyetherimides, polyurethanes, polyureas, polybenzimidazole,polybenzoxazoles, polyimines, polycarbonates, other polyesters, othercopolyesters, and polyamides. In one embodiment, the polymer blend doesnot include polycarbonate. In one embodiment, the polymer blend does notinclude bisphenol polycarbonate. In one embodiment, the polymer blenddoes not include polybutylene terephthalate. In one embodiment, thepolymer blend does not include polyarylene ethers. In one embodiment,the polymer blend does not include cellulose esters.

In certain embodiments for the polymer blend, the at least one otherpolymer is present in the blend in the amount of 50 weight % or less, or40 weight % or less, or 30 weight % or less, or 20 weight % or less, or10 weight % or less, or 5 weight % or less, based on the total weight ofthe blend equaling 100 weight %. In embodiments, the at least one otherpolymer is present in the polymer blend in the amount of 0.01 to 50weight %, or 1 to 50 weight %, or 5 to 50 weight %, or 0.01 to 40 weight%, or 0.01 to 30 weight % or 0.01 to 20 weight %, or 0.01 to 10 weight %or 0.01 to 5 weight %, based on the total weight of the blend equaling100 weight %.

In embodiments, the polymer compositions described herein do not containcarbon nanotubes.

An effective amount of the stabilizing composition can be determined byunderstanding fitness for use requirements, target properties and/ortarget criteria for various applications and/or thermoplastic processingconditions and/or when the chosen property is preserved duringprocessing.

For the purposes of this invention, “aging” refers to any standard knownto one of ordinary skill in the art, and alternatively, is defined asbeing heated for at least three hours at 200° C. or as being heated forat least twenty-four hours at 175° C.

In one embodiment, the polymers or polymer blends useful in theinvention and/or the polymer compositions of the invention, with orwithout toners, can have color values L*, a* and b* which can bedetermined using a Hunter Lab Ultrascan Spectra Colorimeter manufacturedby Hunter Associates Lab Inc., Reston, Va. The color determinations areaverages of values measured on either pellets, or powders or particlesless in size than 300 microns, of the polymers or plaques or other itemsinjection molded or extruded from them. They are determined by theL*a*b* color system of the CIE (International Commission onIllumination) (translated), wherein L* represents the lightnesscoordinate, a* represents the red/green coordinate, and b* representsthe yellow/blue coordinate, as determined by the L*a*b* color systemmeasured following ASTM D 6290-98 and ASTM E308-99.

Unless stated otherwise herein, the color values for this applicationwere measured using polymer powder prepared by cryogenic grinding usingliquid nitrogen in a jet mill to achieve an average particle size in therange from about 50 to 200 microns. The color was measured by weighingout approximately 50 grams of powdered material and placing it into a60×15 mm Petri culture dish. The dish was sealed and the color valueswere determined using a Macbeth Spectrophotometer in reflectance mode,as determined by the L*a*b* color system measured following ASTM D6290-98 and ASTM E308-99.

In certain embodiments, the initial b* color values and/or Δb* colorvalues for the polymers useful in the invention, with or without thepresence of dyes/colorants, can be present in one of the followingranges: −10 to 10; −10 to 9; −10 to 8; −10 to 7; −10 to 6; −10 to 5; −10to 4; −10 to 3; −10 to 2; from −5 to 9; −5 to 8; −5 to 7; −5 to 6; −5 to5; −5 to 4; −5 to 3; −5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1to 4; 1 to 3; and 1 to 2.

The initial b* color value of the polymers tested useful in theinvention was measured prior to aging (i.e., heating) (forsemi-crystalline polymers/polyesters) but after being heated at 200° C.for 15 minutes (for amorphous polymers/polyesters). The Δb* color valuefor the polymer compositions useful in the invention is the differencebetween the initial b* color value and the final b* color value afteraging.

The initial b* color values and/or the Δb* color values for the polymersuseful in the invention can be present in one of the following ranges:less than 10, or less than 9, or less than 8, or less than 7, or lessthan 6, or less than 5, or less than 4, or less than 3, or less than 2,or less than 1, according to the L*, a* and b* color system of the CIE(International Commission on Illumination); the Δb* color values for allpolymers useful in the invention are measured after being heated for atleast three hours at 200° C. or, alternatively, after being heated forat least twenty-four hours at 175° C., according to the L*, a* and b*color system of the CIE (International Commission on Illumination).

In one embodiment, the initial b* color value for the polymers useful inthe invention is less than 5 and the Δb* color value is less than 5 ofsaid polymer composition.

In one embodiment, the initial b* color value for the polymers useful inthe invention and the Δb* color value of said polymer composition isless than 10, or less than 9, or less than 8, or less than 7, or lessthan 6, or less than 5, or less than 4, or less than 3, or less than 2,or less than 1.

In one embodiment, the initial color of the polymer itself is white oropaque.

Zero shear viscosity is useful in some applications where fast polymerflow during/after rapid heating of the polymer is important. The zeroshear viscosities of the polymer compositions useful in the inventioncan be in the following ranges: the final polymer has zero shearviscosity of 100 to 1,000,000 poise at 170° C. to 325° C., or at 300° C.to 325° C. Zero shear viscosity, as used herein, is determined by ASTMD4440 at a shear-rate of 1 1/s. The addition of the antioxidants canlower the zero-shear viscosity of the polymers thus improving theirability to flow more readily in certain processes including ones inwhich they are not subjected to external force to form them into anarticle.

In embodiments, the polymer composition described herein can have a lossin inherent viscosity of 10% or less, or 9% or less, or 8% or less, or7% or less, or 6% or less, or 5% or less, or 4% or less, or 3% or less,after being heated either for at least three hours at 200° C. or,alternatively, after being heated for at least twenty-four hours at 175°C.

In one embodiment, the melt viscosities of the polymer useful in theinvention can be in the following ranges: a melt viscosity of from about100 to 1,000,000 poise as measured at 170° C. to 325° C. or at 250° C.to 300° C. at a shear rate of 10 1/s as determined using ASTM D4440.

In one embodiment, the polymer compositions of the inventionunpredictably undergo equal to or less than a 10% loss of either numberaverage molecular weight (Mn) or weight average molecular weight (Mw)after being heated for at least three hours at 200° C. when used incombination with the primary antioxidants, the secondary antioxidants,the chain extenders and the polymers useful in the invention. This isespecially useful in end-use applications requiring extended heatingconditions such as those requiring heating for at least three hours at200° C. or after being heated for at least twenty-four hours at 175° C.

In one embodiment, the polymer compositions of the inventionunpredictably undergo equal to or less than a 10% loss of either numberaverage molecular weight (Mn) or weight average molecular weight (Mw)after being heated for at least three hours at 200° C. or after beingheated for at least twenty-four hours at 175° C. when the polymersuseful in the invention are used in combination with the primaryantioxidants, the secondary antioxidants, and the chain extenders usefulin the invention.

In one aspect, the polymer composition(s) of the invention can have aloss in weight average molecular weight (Mw) or number average molecularweight (Mn) of 10% or less, or 9% or less, or 8% or less, or 8% or less,or 7% or less, or 6% or less, or 5% or less, or 4% or less or 3% orless, after being heated for at least three hours at 200° C. or,alternatively, after being heated for at least twenty-four hours at 175°C.

In one aspect, the polymer composition(s) of the invention can have aloss in inherent viscosity, of 10% or less, or 9% or less, or 8% orless, or 8% or less, or 7% or less, or 6% or less, or 5% or less, or 4%or less, or 3% or less, after being heated either for at least threehours at 200° C. or, alternatively, after being heated for at leasttwenty-four hours at 175° C.

In one aspect, the polymer composition(s) of the invention can have acombination of: (1) a Δb* color value less than 10 or less than 5according to the L*, a* and b* color system of the CIE (InternationalCommission on Illumination) and (2) a loss in weight average molecularweight (Mw) or number average molecular weight (Mn) of 10% or less,after being heated for at least three hours at 200° C. or,alternatively, after being heated for at least twenty-four hours at 175°C.

In one aspect, the polymer composition(s) of the invention can have acombination of: (1) a Δb* color value less than 10 or less than 5 orless than 3 or less than 2 according to the L*, a* and b* color systemof the CIE (International Commission on Illumination) and (2) a loss ininherent viscosity of 10% or less or 5% or less or 3% or less, afterbeing heated for at least three hours at 200° C. or, alternatively,after being heated for at least twenty-four hours at 175° C.

In one embodiment, the average number of carboxyl end groups present onthe condensation polymer useful in the invention is 20 or less, or 19 orless, or 18 or less, or 17 or less, or 16 or less, or 15 or less, or 14or less, or 13 or less, or 12 or less, or 11 or less, or 10 or less, or9 or less, or 8 or less, or 8 or less, or 7 or less, or 6 or less, or 5or less, or 4 or less, or 3 or less, after being heated either for atleast three hours at 200° C. or, alternatively, after being heated forat least twenty-four hours at 175° C. In one embodiment, the polymercomposition(s) of the invention can have said carboxyl end groupsnumbering 20 or less, 15 or less, 10 or less, 6 or less, 5 or less, or,3 or less, after being heated either for at least three hours at 200° C.or, alternatively, after being heated for at least twenty-four hours at175° C.

In one aspect, the polymer composition(s) of the invention can have acombination of: (1) a Δb* color value less than 10 or less than 5 orless than 3 or less than 2 according to the L*, a* and b* color systemof the CIE (International Commission on Illumination), (2) a loss ininherent viscosity of 10% or less or 5% or less or 3% or less, and (3)average number of carboxyl end groups of 20 or less, 15 or less, 10 orless, or 6 or less, or 5 or less, after being heated either for at leastthree hours at 200° C. or, alternatively, after being heated for atleast twenty-four hours at 175° C.

In one aspect, the polymer composition(s) of the invention can have acombination of: (1) a Δb* color value less than 10 or less than 5 orless than 3 or less than 2 according to the L*, a* and b* color systemof the CIE (International Commission on Illumination), (2) a loss inweight average molecular weight (Mw) or number average molecular weight(Mn) of 10% or less, and (3) a zero shear viscosity of 100 to 1,000,000poise as measured at 170° C. to 325° C., after being heated for at leastthree hours at 200° C. or, alternatively, after being heated for atleast twenty-four hours at 175° C.

In one aspect, the polymer composition(s) of the invention can have acombination of: (1) a Δb* color value less than 10 or less than 5 orless than 3 or less than 2 according to the L*, a* and b* color systemof the CIE (International Commission on Illumination), (2) a loss ininherent viscosity of 10% or less or 5% or less or 3% or less, (3)average number of carboxyl end groups of 20 or less, 15 or less, 10 orless, or 6 or less, or 5 or less, and (4) a melt viscosity of from 100poise to 1,000,000 poise measured at 170° C. to 325° C., the latterbeing measured using ASTM Method D4440, after being heated either for atleast three hours at 200° C. or, alternatively, after being heated forat least twenty-four hours at 175° C.

For the purposes of this invention, the polymers of the invention can besemicrystalline, or amorphous. Degree of crystallinity is measuredherein by differential scanning calorimeter (DSC) using ASTM MethodD3418 and is determined by a DSC curve and the difference in theenthalpy of crystallization exotherm and the enthalpy of fusion(melting) endotherm, as illustrated further below, and is reportedherein as percent crystallinity.

The degree of crystallization can be determined using a Perkin-ElmerModel DSC-2 differential scanning calorimeter and plotting heat flowversus temperature using a 7.5 mg sample and heating the sample in N2purge at 20° C./min from RT to 325° C. The degree of crystallization isdetermined from the plot by calculating the area of the crystallizationpeak above the steady state heat flow and the area of the melting peakbelow the steady state heat flow, calculating the difference in areasand dividing by a constant based on the theoretical heat of fusion for100% crystalline, e.g. for PCTA (29 cal/g). An example of a degree ofcrystallization calculation is shown in FIG. 1. A review of FIG. 1,reveals that points A and B, and intersect C, was determined by drawinga straight line along the steady state portions of the curve, measuringthe area of crystallization peak at 154° C. between points A & C(Hc=3.326 cal/g), measuring the area of melting peak at 225° C. betweenpoints B & C (Hf=6.837 cal/g), and calculating the sample by theequation: % crystallinity=(Hf-Hc)/29=(6.837-3.326)/29100%=12.1%crystallinity.

For purposes of this application, an amorphous polymer refers to apolymer having a degree of crystallinity below 1%. For purposes of thisapplication crystalline polymer and semi-crystalline polymer are usedinterchangeably and refer to a polymer having a degree of crystallinityof 1% or greater. The polymers useful in this invention can have aninitial level of crystallinity of from 1% to 100%, where the intiallevel is measured before being heated. Certain polymers useful in thisinvention can have a final crystallinity of from 1% to 60%, where thefinal crystallinity is measured after being heated either for at leastthree hours at 200° C. or, alternatively, after being heated for atleast twenty-four hours at 175° C. In other embodiments, the polymersuseful in this invention can have a final crystallinity of from 1 to40%.

The polymers useful in this invention can have a crystalline meltingpoint of from 165° to 350° C.; from equal to or greater than 280° C.;from equal to or greater than 275° C.; from equal to or greater than270° C.; from equal to or greater than 255° C.; or from equal to orgreater than 250° C.; or from equal to or greater than 200° C., or fromequal to or greater than 170° C. as measured by differential scanningcalorimetry (DSC) at 20° C./minute according to ASTM Method 3418.

The isothermal crystallization temperature is described, for example, inElias, H. Macromolecules, Plenum Press: NY, 1977, p 391. Thecrystallization half-time is determined as the time span from reachingdifferent isothermal crystallization temperatures to the point of acrystallization peak on the DSC curve.

In one aspect, certain polymers useful in the present invention can havecrystallization half-times from greater than 0 up to and including 5minutes. In one aspect, certain polymers useful in the present inventioncan have crystallization half-times greater than 5 minutes.

In another embodiment, the invention further relates to articles ofmanufacture comprising any of the polymers and blends described above.

The present invention could have usefulness in multiple applications.Areas that could benefit are applications that are at high temperaturesand humidity levels for extended periods of time. These could includeapplications in the 3D printing of thermoplastic powders, additiveprinting and/or additive manufacturing, powder coating of metalarticles, LED lighting, filtration media, electrical and electronic,under the hood automotive applications, maritime, aerospace,thermoplastic powder coatings and the chemical process industries,surgical simulation devices, and orthotic and prosthetic devices. Incertain embodiments, the article of manufacture can comprise at leastone light emitting diode (LED) assembly housing, or reflector. Inembodiments, the article of manufacture comprises at least one 3D powderor material used to make a different article of manufacture. Inembodiments, the article of manufacture is a molded or extruded article.

In embodiments, the article of manufacture is a fiber or a filament. Inembodiments, the article of manufacture is a film or sheet

Lower shear melt viscosities are very useful for 3-D printingapplications where fast polymer flow from the rapid heat up of thepolymer from a laser or infrared heat source is helpful to ensuring awell-formed and fused article.

In 3D printing, several processing methods are used which include HighSpeed Sintering (HSS) and Selective Laser Sintering (SLS). In the caseof the HSS process, powdered thermoplastic polymers are heated using aninfrared (IR) heat lamp to create useful objects or in the SLS process,a CO2 laser is used to heat the powders. To speed up the printingprocess, the powders are often held at very high temperatures just belowtheir melting point for up to 24 hours to minimize the heat output fromthe IR lamp. Polymers held at these high temperatures and times canundergo thermal oxidative degradation and hydrolytic degradation, ifthey are a condensation polymer. This can cause the molecular weight todrop and the polymer to discolor and render it unrecyclable andun-processable.

Furthermore, in processes such as 3-D printing from powders andtraditional powder coating of metals, the ability to flow and create ahomogenous article with no other force than gravity or surface tensionis helpful in creating useful and aesthetically pleasing articles.

The use of light emitting diodes (LED) has become increasingly common inlighting applications in recent years. LEDs benefit from high efficiencycompared to traditional light sources and can be designed to operate forextremely long periods of time. As such, LEDs require materials ofconstruction that can also survive for long periods of time withoutdegrading or losing their efficacy in these applications. Compoundedplastic materials are used as reflector materials in the construction ofLEDs both to provide control over the direction of emitted light as wellas to protect the actual diode from damage. These compounded plasticmaterials can be thermoplastic or thermoset based on the needs of theLED in the application. For example, high power LEDs, with energy inputrequires >1.0 watts typically use thermoset materials due to the heatgenerated in use. Lower wattage LEDs can use thermoplastic materialsthat can be injection molded. These injection molded materials arecheaper to process and can include a range of conventional materials.During the assembly of LEDs, the diode is soldered to the LEAD frame andthis soldering process requires that the thermoplastic materials aredimensionally stable during the soldering process. This requires thatmaterial to be semi-crystalline with a crystalline melting point inexcess of 280° C. Additionally, since these molded thermoplastic partsreflect the LED light from the diode, they can provide high reflectivityduring the lifetime of the application. Low color and high colorstability, measured via color measurements as described herein, beforeand after aging, is often used as a proxy for reflectivity. In certainembodiments, these parts also have high mechanical properties becausethey protect the diode from damage and survive various processing stepswithout breaking. The properties of reflectivity and high mechanicalstrength can be improved by compounding various base resin with otheradditives. These additives can provide enhanced “whiteness” as is thecase for titanium dioxide and they can provide high toughness as is thecase for inorganic fillers like glass fiber. Stabilizers and nucleatingagents can also be added to improve stability and increase the rate ofcrystallization respectively. Due to the high demands of thethermoplastic materials in these applications, PCT is currently used inlarge amounts for the thermoplastic LED applications. PCT has acrystalline melting point of 285° C. and is manufactured carefully toproduce a material with very low color (high reflectivity). PCT can becompounded with titanium dioxide and glass fiber along with variousstabilizers and additives to optimize the performance of this materialin these applications. US Patent Application 2007/0213458 discloses theuse of PCT compounds in Light-Emitting Diode Assembly Housings.

During the manufacture of injection molded articles, the thermoplasticresin undergoes thermal and shear induced degradation. Additionally,waste material that is not converted into usable parts should berecycled to reduce to overall cost of the material. For these reasons,the compounded thermoplastic material much be stable to processingwithout significant loss of the original performance. Additionally, themolded parts should maintain high reflectivity and high mechanicalstrength throughout the lifetime of the application, which in the caseof LEDs, could be as long as 20+ years. This invention describes anoptimized combination of additives that improves the process robustnessof the compounded PCT resins. Improvements in reflectivity are measuredvia color and color stability using the color measurement as describedherein. Reprocessability is measured via inherent viscosity (IV) beforeand after an extrusion or processing step.

In another embodiment, the invention further relates to articles ofmanufacture comprising any of the polymers, polymer compositions orpolymer blends described above.

The methods of forming the polymers into articles of manufacture,fibers, films, molded articles, containers, and sheeting are well knownin the art. The polyester compositions are useful in articles ofmanufacture including, but not limited to, fibers, filaments, films,sheets, containers, extruded, calendered, and/or molded articlesincluding, but not limited to, injection molded articles, extrudedarticles, cast extrusion articles, profile extrusion articles, melt spunarticles, thermoformed articles, extrusion molded articles, injectionblow molded articles, injection stretch blow molded articles, extrusionblow molded articles and extrusion stretch blow molded articles. Thepolyester compositions useful in the invention may be used in varioustypes of film and/or sheet, including but not limited to extrudedfilm(s) and/or sheet(s), calendered film(s) and/or sheet(s), compressionmolded film(s) and/or sheet(s), solution casted film(s) and/or sheet(s).Methods of making film and/or sheet include but are not limited toextrusion, calendering, compression molding, and solution casting. Thepolymer compositions and/or polymer blend compositions can be useful informing fibers, films, light diffusing articles, light diffusing sheets,light reflecting articles, light reflecting sheets, light emittingdiodes, 3D powders or other materials, 3D articles containing powders orother materials. The extruded sheet can be further modified usingtypical fabrication techniques such as thermoforming, cold bending, hotbending, adhesive bonding, cutting, drilling, laser cutting, etc. tocreate shapes useful for application as light reflectors and/or lightdiffusers.

In one embodiment, the light reflector article comprising the polymercompositions of the invention can comprise at least one inorganic lightreflecting additive, for example, titanium dioxide, barium sulfate,calcium carbonate or mixtures thereof.

Other end-use applications that can employ the polymer compositions ofthe invention include but are not limited to: (1) membrane backing. Itcan be a film or a woven or nonwoven (wetlaid or melt blown/melt spun)mat. Improved temperature, chemical resistance, and/or hydrolyticresistance would be relevant to it as well; (2) spun-laid nonwoven websusing processes well known in the art such as meltblowing and spun bondprocesses, wherein the continuous PCT fiber is spun from a pellet andlaid into a nonwoven fabric in a single processing step; dry-laid orwet-laid nonwoven webs using processes well known in the art such ascarding or air-laid processes, wherein PCT fiber is first spun in oneprocess, chopped into staple fiber and laid into nonwoven fabric in asecondary step, using dry-laying technologies; Such nonwoven webs can beuseful for air and liquid filtration media, particularly thosefiltration applications which are routinely exposed to high temperatures(80-200 C) or corrosive chemicals. Wet laid webs is a common method forproducing filtration media.

Machine clothing comprising monofilament, multifilament fibers, films orsheet, with improved thermal stability over existing PCT, PCT copolymersand additive formulations, to enable use in high temperaturemanufacturing environments, including for example belts used in thedryer section of paper and tissue making processes. Dry-laid media caninclude high temperature and/or chemically resistant bag house filtersand variation thereof used to capture pollutants, such as those in incoal burning power plants, and various manufacturing processes.

Certain embodiments would include using the polymer compositions of theinvention in film application. Film substrates with enhanced stabilityto high temperature processes and use conditions. High temperatureprocesses may include variations of lead free soldering processes onfilms requiring good registration, flexibility, and/or optical clarity,as standalone or part of a multilayer system that may include inks,coatings, and/or other functionality.

As used herein, the abbreviation “wt” means “weight”. The inherentviscosity of the polymers, for example, the polyesters was determined in60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100ml at 25° C.

The following examples further illustrate how the compositions of matterof the invention can be made and evaluated, and are intended to bepurely exemplary of the invention and are not intended to limit thescope thereof. Unless indicated otherwise, parts are parts by weight,temperature is in degrees C. or is at room temperature, loading level ismeasured in units of weight percentage based on the total weight of theinitial polymer composition equaling 100 weight %; and pressure is at ornear atmospheric.

It can be clearly seen from a comparison of the data in the aboverelevant working examples that the combination of the primaryantioxidants, secondary antioxidants and chain extending agents usefulin the invention within a certain loading level can improved oxidativestability, color and flow of the certain polymers.

The invention has been described in detail with reference to theembodiments disclosed herein, but it will be understood that variationsand modifications can be affected within the scope of this invention.

EXAMPLES

The following abbreviations apply throughout the working examples andspecification:

Abbreviation Table Abbreviation or Term Description AO Antioxidant a* Asdefined according to the L*, a* and b* color system of the CIE(International Commission on Illumination) b* As defined according tothe L*, a* and b* color system of the CIE (International Commission onIllumination) Final b* color b* color value after aging (after beingheated for at least three hours at 200° C. or after being heated for atleast twenty-four hours at 175° C.). Initial b* or For the data inTables 1-7, initial b* color value is Starting b* measured after it isplaced in an oven at 200° C. for 15 minutes; For the data in Table 8-14,the initial b* color value of said polymer is measured prior to heating.CEG Carboxyl end groups were measured via titration da* Difference in a*db* Difference in b* De Total color difference dL* or ΔL* Difference inL* Delta b* (Δb*); Change in b* value = difference between initial b**final b*; *aged b** value and final b*value Design Expert Statisticalsoftware described below Irganox ™1010— Irganox ™1010—pentaerythritoltetrakis[3,5-di-t- primary antioxidant butyl-4-hydroxyphenyl)propionateIrgafos ™ 168— Irgafos ™168—tris(2,4-di-tert-butylphenyl) secondaryphosphite antioxidant Joncryl ™ 4468 Styrene glycidyl-methacrylate chainextending agent Mw Weight average molecular weight Mn Number averagemolecular weight Mz z-Average Molar Mass; higher average molecularweight (Mz)) PCT A polyester comprising 100 mole % of 1,4-cyclohexanedimethanol residues, and 100 mole % terephthalic acidresidues; poly(cyclohexylenedimethylene) terephthalate (PCT) Polyester 1A copolyesterether (PCCE) comprising: 49.5 mole%—1,4-benzenedicarboxylic acid, dimethyl ester, 0.5 mole%—1,3-dihydro-1,2dioxo-5- isobenzofurancarboxylic acid (TMA), 41.1 mole% 1,4-cyclohexanedimethanol, and 8.9 mole % poly(tetramethylene ether)glycol, having an inherent viscosity of 1.16 dUg Polyester 2 Descriptionis in Table 8; PCT having an inherent viscosity of 0.772 dUg PDPolydispersity Index (Mw/Mn) IV or I.V. Inherent viscosity as definedherein dL/g Deciliters per gram % Percentages are by weight unlessotherwise specified L* As defined above R² Coefficient of determinationAdjusted R² Modified R² that is adjusted for the number of predictors inthe model. Wt. % Weight percent as described herein

Two different types of polymers, an elastomer and a rigid polyesterthermoplastic, were evaluated in the present invention and were preparedusing two different methods due to the particular processingcharacteristics of the polymers.

The stabilized elastomer blends were made by using Polyester 1, a PCCEavailable from Eastman Chemical Company. Pellets of Polyester 1 werepre-dried overnight for at least 4 to 8 hours. Blends of Polyester 1 andstabilizing additives (Irganox™ 1010, Irgafos™ 168, Joncryl™ 4468) wereweighed on an analytical scale, mixed together and then added to aBrabender Intelli-Torque batch mixer. A batch size of 260 grams wasused, the mixer body was set at 230° C. and the mixer blade rotationspeed was set at 40 rpm. Each sample was run until the temperaturereached approximately 220° C. The mixer was then stopped and the mixtureremoved from the mixer. Samples were then cryogenically pulverized intoa powder form with particle size less than 300 microns. The powders werethen placed in glass jars with the lids removed and put into a forcedconvection oven set at 170° C. Jars were removed at 1, 2, 4, 8 and 20hours. Color measurements, both visually and with a spectrophotometerwere made, and molecular weight and inherent viscosity were measuredusing gel permeation chromatography.

The stabilized PCT blends were made by using Polyester 2 or Polyester 3commercially available from Eastman Chemical Company, Kingsport, Tenn.Samples were predried at 70° C. and then added to a Prism twin screwextruder set at 315° C. The screws were run at 40 rpm. After compoundingthe blends, 20 grams of pellets were added to shallow aluminum pans andplaced in a forced air convection oven set at 200° C. for 15 minutes tocrystallize the pellets. These pellets were used to determine theinitial color measurement (initial b*). Another 20 grams of pellets wereadded to shallow aluminum pans and placed in a forced air convectionoven set at 200° C. for 3 hours. Molecular weight was measured via gelpermeation chromatography, inherent viscosity was measured with aviscometer, and carboxyl end groups were determined via titration.

The following tables and figure summarize experimental results of theinvention:

TABLE 1 Polyester 1 with Irganox ™1010 and Irgafos ™168-GPC and Colorresults—Oven Aging at 170° C.* FORMULATION- FACTORS (% = weight %)MOLECULAR Run Irganox ™ Irgafos ™ WEIGHT DATA COLOR DATA Number 1010 168Polyester1 Mn Mw Mz PD L* a* b* dL* da* db* De 25-1 0.000% 0.000%100.000% 89.37 1.88 12.97  1 hour 0.000% 0.000% 100.000% 9961 3047858696 3.06 89.33 0.77 15.07 −0.04 −1.11 2.1 2.38  2 hours 0.000% 0.000%100.000% 9075 27379 52635 3.017 88.55 −1.01 20.6 −0.82 −2.89 7.63 8.2  4hours 0.000% 0.000% 100.000% 2281 11875 24981 5.206 94.89 −0.33 11.485.52 −2.21 −1.49 6.13  8 hours 0.000% 0.000% 100.000% 1238 8857 353577.154 85.97 3.13 25.4 −3.4 1.25 12.43 12.95 20 hours 0.000% 0.000%100.000% 750 6439 20510 8.585 76.71 7.45 29.64 −12.66 5.57 16.67 21.6625-2 0.250% 0.125%  99.625% 88.94 2.15 15.45  1 hour 0.250% 0.125% 99.625% 11845 30358 54002 2.563 90.1 1.94 14.5 1.16 −0.21 −0.95 1.51  2hours 0.250% 0.125%  99.625% 10388 30622 60636 2.948 89.77 1.79 15.160.83 −0.36 −0.29 0.95  4 hours 0.250% 0.125%  99.625% 8466 28854 519293.408 88.81 0.85 20.07 −0.13 −1.3 4.62 4.8  8 hours 0.250% 0.125% 99.625% 7102 24388 53159 3.434 85.68 1.75 26.94 −3.26 −0.4 11.49 11.9520 hours 0.250% 0.125%  99.625% 1640 9806 29817 5.979 85.99 3.45 25.59−2.95 1.3 10.14 10.64 25-3 0.500% 0.250%  99.250% 89.65 1.85 15.22  1hour 0.500% 0.250%  99.250% 9615 29795 53576 3.099 88.97 2.47 14.63−0.68 0.62 −0.59 1.09  2 hours 0.500% 0.250%  99.250% 9035 30099 551503.331 89.14 2.51 16.12 −0.51 0.66 0.9 1.23  4 hours 0.500% 0.250% 99.250% 9782 29923 57315 3.059 86.74 3.11 20.16 −2.91 1.26 4.94 5.87  8hours 0.500% 0.250%  99.250% 5814 23747 40621 4.084 84.23 2.76 26.71−5.42 0.91 11.49 12.74 20 hours 0.500% 0.250%  99.250% 2688 11392 281664.238 90.5 1.28 19.34 0.85 −0.57 4.12 4.25 25-4 1.000% 0.500%  98.500%91.04 1.76 13.74  1 hour 1.000% 0.500%  98.500% 13420 29677 58886 2.21192.21 1.5 11.92 1.17 −0.26 −1.82 2.18  2 hours 1.000% 0.500%  98.500%12878 29951 49498 2.326 91.01 2.09 13.72 0.03 −0.33 −0.02 0.33  4 hours1.000% 0.500%  98.500% 6070 28932 53492 4.766 89.57 2.79 14.9 1.47 −1.031.16 2.14  8 hours 1.000% 0.500%  98.500% 5971 29202 55726 4.891 87.823.2 18.86 3.22 −1.44 5.12 6.22 20 hours 1.000% 0.500%  98.500% 680923417 43965 3.439 82.57 4.29 30.9 8.47 −2.53 17.16 19.30 *Table 1 showsthat a conventional combination of a primary antioxidant (Irganox 1010)and a secondary antioxidant (Irgafos 168), while improving thermalstability to some extent, does not prevent degradation or greatly reducethe change in color.

TABLE 2 Polyester 1 with Irganox 1010 ™, Irgafos ™168 andJoncryl ™4468-GPC and Color results—Oven Aging at 170° C.* FORMULATIONSFACTORS Irga- Irga- MOLECULAR Run nox ™ fos ™ Joncryl ™ Poly- WEIGHTDATA COLOR DATA Number 1010 168 4468 ester 1 Mn Mw Mz PD L* a* b* dL*da* db* dE 25-5 1.000% 0.500% 0.600% 97.900% 7929 35417 94202 4.467 93.2−0.49 3.99  1 hour 1.000% 0.500% 0.600% 97.900% 7716 35400 98674 4.588 2 hours 1.000% 0.500% 0.600% 97.900% 8248 36699 115745 4.449  4 hours1.000% 0.500% 0.600% 97.900% 7986 36690 113414 4.594  8 hours 1.000%0.500% 0.600% 97.900% 8531 39947 155293 4.683 20 hours 1.000% 0.500%0.600% 97.900% 7865 46731 320096 5.942 90.29 −0.73 14.15 −2.91 −0.2510.16 10.57 25-6 1.000% 0.500% 1.000% 97.500% 7287 34627 90553 4.75293.2 −0.49 3.99  1 hour 1.000% 0.500% 1.000% 97.500% 7729 35405 982214.581  2 hours 1.000% 0.500% 1.000% 97.500% 7425 36003 106503 4.849  4hours 1.000% 0.500% 1.000% 97.500% 7591 38281 134480 5.043  8 hours1.000% 0.500% 1.000% 97.500% 7238 39405 158091 5.444 20 hours 1.000%0.500% 1.000% 97.500% 7716 53043 491647 6.874 92.16 −0.89 10.93 −1.04−0.4 6.94 7.03 25-7 1.000% 0.500% 1.400% 97.100% 7341 34879 95374 4.75193.2 −0.49 3.99  1 hour 1.000% 0.500% 1.400% 97.100% 7371 35835 1039064.862  2 hours 1.000% 0.500% 1.400% 97.100% 7840 36645 107961 4.674  4hours 1.000% 0.500% 1.400% 97.100% 7154 41465 193510 5.796  8 hours1.000% 0.500% 1.400% 97.100% 7867 43509 228978 5.531 20 hours 1.000%0.500% 1.400% 97.100% 6991 52718 479743 7.541 91.9 −1.13 12.63 −1.3−0.64 8.64 8.76 *Table 2 shows that with the incorporation Joncryl 4468retains molecular weight and greatly reduces the amount of color change.Mn and Mw either stay the same or increase. The total color change ismuch less than the readings in Table 1.

TABLE 3 Pilot Plant Scale up—Polyester 1 with Irganox ™1010,Irgafos ™168 and Joncryl ™4468—Color results—24 hours Oven Aging at 175°C.* FACTORS FORMULATIONS MOLECULAR Irganox ™ Irgafos ™ Joncryl ™ WEIGHTDATA COLOR DATA 1010 168 4468 Polyester 1 Mn Mw Mz PD L* a* b* dL* da*db* dE No AO    0%    0%    0% 100.00%  7707 18101 31838 2.349 With AO1.000% 0.500% 0.500% 98.000% 14164 31126 58971 2.198 92.61 −0.58 9.33−0.59 −0.09 5.34 5.38 *Table 3 shows an optimized formulation that hasbeen compounded on a pilot scaled compounding line and the retention ofmolecular weight and improved color.

TABLE 4 Polyester 1 with Irganox 1010 ™, Irgafos ™168 and Joncryl ™4468,Zero Shear Viscosity Results. VISCOSITY VISCOSITY NO WITH TEMPERATUREANTIOXIDANTS ANTIOXIDANTS C (MPA) (MPA) 249.73 5105 4668.5 248.82 5289.14789 247.49 5539.4 5008.6 245.17 5991.4 5271.3 242.84 6443 5500.7 241.456732.1 5817.9 239.87 7088.4 6024.1 238.54 7396.4 6231.4 236.93 7806.16459.7 235.65 8119.5 6662.1 234.24 8491.7 6885.9 233.14 8801.2 7130.2232.05 9106.6 7373.1 230.62 9495 7602 228.87 10026 7846.3 227.4 104548089 226.17 10841 8341.8 224.96 11230 8601.4 223.73 11632 8865.4 222.512038 9138.3 221.28 12452 9418 220.06 12878 9705.6 218.85 13312 10050217.64 13765 10417 216.44 14226 10748 215.21 14704 11074 213.97 1518911414 212.75 15690 11759 211.54 16203 12115 210.31 16731 12485 208.7717391 12867 207.34 18017 13262 206.12 18634 13662 204.9 19219 14082203.69 19821 14510 202.45 20438 14954 201.25 21080 15424 199.66 2191615898 198.27 22636 16385 197.06 23399 16892 195.84 24125 17415 194.6224865 17960 193.4 25623 18517 192.18 26414 19094 190.95 27225 19700189.74 28055 20323 188.52 28920 20951 187.3 29800 21627 186.08 3071122313 184.87 31657 23028 183.65 32637 23765 182.43 33652 24533 181.234692 25328 179.98 35777 26173 178.77 36906 27056 177.55 38077 27991176.32 39309 28985 175.07 40555 30073 173.87 41876 31269 172.64 4327732648 171.43 44740 34293 170.21 46306 36321 168.99 47972 38965 167.7649772 42666 166.54 51724 48125 165.32 53899 66486 164.12 56383 1.22E+06162.88 59277 161.19 64002 159.4 70683 158.18 77021 156.01 93850 153.981.21E+05 151.95 1.77E+05 150.3 2.70E+05 148.71 4.44E+05 147.37 7.03E+05144.8 1.91E+06 143.65 2.96E+06 *Table 4 shows the effect of theanti-oxidant additives on zero shear viscosity, an important attributein 3-D printing powders where the polymer can flow without any externalforces other than gravity and surface tension.

TABLE 5 Polyester 1 with Irganox 1010 ™, Irgafos ™168 andJoncryl ™4468—GPC and Color results—Oven Aging at 170° C.* FormulationsFACTORS Run Poly- Irga- Irga- Jon- Molecular Num- ester nox fos crylWeight Data Color Data ber Time 1 1010 168 4468 Mn Mw Mz PD L* a* b* dL*da* db* DE 1 0 98.500% 1.000% 0.000% 0.500% 8422 34362 89987 4.08 93.52−0.49 3.93 hours 1 98.500% 1.000% 0.000% 0.500% 9713 32944 68318 3.39hour 2 98.500% 1.000% 0.000% 0.500% 7285 36745 115524 5.04 hours 498.500% 1.000% 0.000% 0.500% 8268 38424 132133 4.65 hours 8 98.500%1.000% 0.000% 0.500% 8542 42099 188783 4.93 hours 20 98.500% 1.000%0.000% 0.500% 8952 42145 291675 4.71 84.6 2.34 27.38 2.83 23.46 25.2627.13 hours 2 0 98.250% 1.000% 0.250% 0.500% 8282 32148 66326 3.88 93.52−0.49 3.93 hours 1 98.250% 1.000% 0.250% 0.500% 8495 35719 146409 4.2hour 2 98.250% 1.000% 0.250% 0.500% 8447 38621 175798 4.57 hours 498.250% 1.000% 0.250% 0.500% 9360 39949 199366 4.27 hours 8 98.250%1.000% 0.250% 0.500% 8124 43279 228716 5.33 hours 20 98.250% 1.000%0.250% 0.500% 7820 48041 371326 6.14 88.77 1.11 19.25 1.6 15.32 16.1217.65 hours 3 0 98.000% 1.000% 0.500% 0.500% 7091 35435 165233 5 93.52−0.49 3.93 hours 1 98.000% 1.000% 0.500% 0.500% 7146 38387 232072 5.37hour 2 98.000% 1.000% 0.500% 0.500% 7624 37155 191737 4.87 hours 498.000% 1.000% 0.500% 0.500% 7894 39416 202947 4.99 hours 8 98.000%1.000% 0.500% 0.500% 7038 44166 311159 6.28 hours 20 98.000% 1.000%0.500% 0.500% 7261 49935 414672 6.88 89.28 0.45 17.9 0.94 13.97 14.6316.04 hours 4 0 98.500% 1.000% 0.500% 0.000% 7142 29735 75542 4.16 93.52−0.49 3.93 hours 1 98.500% 1.000% 0.500% 0.000% 6819 30875 63862 4.53hour 2 98.500% 1.000% 0.500% 0.000% 6809 31616 99208 4.64 hours 498.500% 1.000% 0.500% 0.000% 7192 31883 90469 4.43 hours 8 98.500%1.000% 0.500% 0.000% 6687 31235 136411 4.67 hours 20 98.500% 1.000%0.500% 0.000% 6894 25504 88108 3.7 77.92 6.49 32.86 6.98 28.93 33.6 34.4hours 5 0 98.333% 1.000% 0.500% 0.167% 7563 32290 77768 4.27 93.52 −0.493.93 hours 1 98.333% 1.000% 0.500% 0.167% 7379 33829 116545 4.58 hour 298.333% 1.000% 0.500% 0.167% 8518 37726 186898 4.43 hours 4 98.333%1.000% 0.500% 0.167% 7359 33742 123426 4.59 hours 8 98.333% 1.000%0.500% 0.167% 7166 38621 223271 5.39 hours 20 98.333% 1.000% 0.500%0.167% 6717 33038 207690 4.92 75.78 6.42 31.38 6.91 27.46 33.41 32.91hours 6 0 98.167% 1.000% 0.500% 0.333% 7246 33590 101821 4.64 93.52−0.49 3.93 hours 1 98.167% 1.000% 0.500% 0.333% 7169 34074 106997 4.75hour 2 98.167% 1.000% 0.500% 0.333% 6931 36213 160621 5.22 hours 498.167% 1.000% 0.500% 0.333% 7036 37673 178436 5.35 hours 8 98.167%1.000% 0.500% 0.333% 7090 41953 261212 5.92 hours 20 98.167% 1.000%0.500% 0.333% 7034 40691 314794 5.78 86.09 2.24 24.32 2.74 20.39 21.8723.61 hours 7 0 99.000% 0.000% 0.500% 0.500% 8496 33621 115362 3.9693.52 −0.49 3.93 hours 1 99.000% 0.000% 0.500% 0.500% 8350 35085 1496124.2 hour 2 99.000% 0.000% 0.500% 0.500% 17830 30823 49842 1.73 hours 499.000% 0.000% 0.500% 0.500% 7876 31466 80815 4 hours 8 99.000% 0.000%0.500% 0.500% 2324 11953 49366 5.14 hours 20 99.000% 0.000% 0.500%0.500% 1575 5528 12517 3.51 47.25 13.79 21.07 46.27 14.29 17.14 51.37hours 8 0 98.667% 0.333% 0.500% 0.500% 7809 33029 72463 4.23 93.52 −0.493.93 hours 1 98.667% 0.333% 0.500% 0.500% 7710 33540 82371 4.35 hour 298.667% 0.333% 0.500% 0.500% 7778 33657 84600 4.33 hours 4 98.667%0.333% 0.500% 0.500% 8486 34485 87048 4.06 hours 8 98.667% 0.333% 0.500%0.500% 8041 36145 114886 4.49 hours 20 98.667% 0.333% 0.500% 0.500% 712331007 134081 4.35 84.08 1.75 28.05 −9.44 2.24 24.12 26 hours 9 0 98.333%0.667% 0.500% 0.500% 7426 32825 80628 4.42 93.52 −0.49 3.93 hours 198.333% 0.667% 0.500% 0.500% 7632 34170 89394 4.48 hour 2 98.333% 0.667%0.500% 0.500% 7734 34629 98438 4.48 hours 4 98.333% 0.667% 0.500% 0.500%8200 36356 117091 4.43 hours 8 98.333% 0.667% 0.500% 0.500% 7498 38973161177 5.2 hours 20 98.333% 0.667% 0.500% 0.500% 7676 41621 242620 5.4288.38 0 18.28 −5.14 0.49 14.35 15.25 hours 10  0 99.500% 0.000% 0.000%0.500% 9684 33737 102960 3.48 93.52 −0.49 3.93 hours 1 99.500% 0.000%0.000% 0.500% 10275 34138 102992 3.32 hour 2 99.500% 0.000% 0.000%0.500% 10037 33856 131734 3.37 hours 4 99.500% 0.000% 0.000% 0.500% 780327622 110068 3.54 hours 8 99.500% 0.000% 0.000% 0.500% 2562 13584 730985.3 hours 20 99.500% 0.000% 0.000% 0.500% 1802 5793 13147 3.22 43.0710.82 14.06 −50.45 11.31 10.13 52.69 hours *Table 5 shows an interactionbetween Irganox ™1010 and Joncryl ™4468 to improve molecular weightretention and color, but the addition of IrgafosTm168 reduces the changein color.

Example 1

Table 1 above contains compositions studied, gel permeationchromatography results and color difference data. Four differentformulations were investigated, control formulation with 100% Polyester1, a formulation with 0.25% Irganox 1010, 0.125% Irgafos 168, and99.625% Polyester 1, a formulation with 0.5% Irganox 1010, 0.25% Irgafos168, and 99.25% Polyester 1, and a formulation with 1.0% Irganox 1010,0.5% Irgafos 168, and 98.5% Polyester 1. After the aging protocol in theforced air oven, the results show that molecular weights (number average(Mn), weight average (Mw) and higher average molecular weight (Mz)decreased less with higher loadings of Irganox 1010 and Irgafos 168.Yellowness (b* and db*) and total color difference (dE) all generallychanged less with higher loadings of Irganox 1010 and Irgafos 168. Therewas some difficulty in obtaining accurate color data as some of thepowder samples fused together and resulted in some inconsistentmeasurements, but FIGS. 1 to 5 above (samples 25-1 to 25-4) visuallyshow the dramatic improvement in reducing color change at higherloadings of Irganox 1010 and Irgafos 168.

Example 2

Table 2 above contains compositions studied, gel permeationchromatography results and color difference data. Three differentformulations were investigated, a formulation with 1.0% Irganox 1010,0.5% Irgafos 168, 0.6% Joncryl 4468 and 97.9% Polyester 1, a formulationwith 1.0% Irganox 1010, 0.5% Irgafos 168, 1.0% Joncryl 4468 and 97.5%Polyester 1, and a formulation with 1.0% Irganox 1010, 0.5% Irgafos 168,1.4% Joncryl 4468 and 97.1% Polyester 1. After the aging protocol in theforced air oven, the results show that molecular weights (number average(Mn), weight average (Mw) and higher average molecular weight (Mz)) allincreased with higher loadings of Irganox 1010 and Irgafos 168. Onlycolor readings were taken at after 20 hours of oven aging. Yellowness(b* and db*) and total color difference (dE) all generally decreasedwith higher loadings of Irganox 1010 and Irgafos 168. There was somedifficulty in obtaining accurate color data as some of the powdersamples fused together and resulted in some inconsistent measurements,but FIGS. 1 to 5 herein (samples 25-5 to 25-7) visually show thedramatic improvement in reducing color change at higher loadings ofIrganox 1010, Irgafos 168 and Joncryl 4468. A visual comparison ofsamples 25-1, 2, 3 and 4 to 25-5, 6 and 7 shows a drastic and unexpectedimprovement in color.

Example 3

Table 3 above contains the results of a pilot plant scale up includinggel permeation chromatography results and color difference data. Oneformulation was run based on Runs 2 and 3 and consisted of 1.0% Irganox1010, 0.5% Irgafos 168, 0.5% Joncryl 4468 and 98.0% Polyester 1. Acontrol formulation with no additives was run as a comparison. Thecomposition was compounded on a production size twin screw compoundingextruder at 215° C. Extruded strands were immediately cooled in a waterbath and then pelletized. Samples were aged in a forced air convectionoven set at 175° C. for 24 hours. The GPC data shows that theformulation with Irganox 1010, Irgafos 168 and Joncryl retainedmolecular weight and had a minimal amount of color change. FIG. 5visually shows the difference in the two formulations.

Example 4

Table 4 herein shows a viscosity comparison of a formulation ofPolyester 1 and a formulation containing 1.0% Irganox™1010, 0.5%Irgafos™ 168, 0.5% Joncryl™ 4468 and 98.0% Polyester 1. A parallel platerheometer measured viscosity at a sweep rate of 1 rad/sec over atemperature range of approximately 150 to 250° C. A frequency sweep of 1rad/sec is the lower limit of the equipment and simulates the zero-shearviscosity of a material, that is, the viscosity of the material uponwhich no shear forces are applied. This is a measure of the resistanceto flow of a material. The data shows that the composition containing1.0% Irganox™ 1010, 0.5% Irgafos™168, 0.5% Joncryl™ 4468 and 98.0%Polyester 1 has a much lower viscosity than the formulation with noadditives. This lower viscosity would be desirable is some applicationswhere fast polymer flow during/after rapid heating of the polymer isimportant.

Example 5

Table 5 herein contains compositions studied, gel permeationchromatography results and color difference data. Ten differentformulations were investigated, formulation with combinations ofIrganox™1010, Irgafos™168, Joncryl™4468 and Polyester 1 at variousloadings. Runs 1, 2, and 3 kept the Irganox™1010 at 1.0%, theJoncryl™4468 at 0.5% and the Irgafos™168 was added at 0.0%, 0.25% and0.5% to Polyester 1 to a total of 100%. Runs 4, 5, and 6 kept theIrganox™1010 at 1.0%, the Irgafos™168 at 0.5% and the Joncryl™4468 wasadded at 0.0%, 0.167% and 0.333% to Polyester 1 to a total of 100%. Runs7, 8, and 9 kept the Irgafos 168 at 0.5%, the Joncryl™4468 at 0.5% andthe Irganox™1010 was added at 0.0%, 0.333% and 0.667% to Polyester 1 toa total of 100%. Run 10 only had Joncryl™4468 at 0.5% added to Polyester1 to a total of 100%. After the aging protocol in the forced air oven,the results show the following: Runs 1, 2 and 3 show that at constantIrganox 1010 and Joncryl™4468 levels, increasing the Irgafos™168improves molecular weight and overall color difference (DE). Runs 3, 4,5, and 6 show that at constant Irgnaox™1010 and Irgafos™168, increasingthe Joncryl 4468 improves the molecular weight and overall color change(DE). Runs 3, 7, 8 and 9 show that at constant Irgfos™168 andJoncryl™4468, increasing Irganox™1010 dramatically improve the molecularweight and overall color change (DE). The difference between runs 3 and7 is striking showing that there is a synergy between the Irganox™1010and the Joncryl™4468. Run 10 shows that Joncryl™4468 on its own has nobeneficial effect.

In the following Examples and Tables, the effect of epoxy chainextending agent and antioxidant combinations withpoly(cyclohexylenedimethylene) terephthalate (PCT) was studied. Anexperimental design was completed to understand the effect of theseadditives on the final material properties of PCT. The design includedPCT plus a combination of additives, each added at a high and a lowlevel. It was unexpectedly found that a 2-way interaction exists betweenthe combination of antioxidant and chain extending agent. In otherwords, the combination of chain extending agent and antioxidant gavesignificant improvements over the addition of either on their own.Additionally, an optimized formulation that included a secondaryantioxidant was identified to maintain IV, reduce carboxyl chain ends,and reduce color in the compound. This optimized formulation contained alow concentration of primary antioxidant, a relatively high level ofsecondary antioxidant, and a relatively high level of chain extendingagent.

Characterization of Polyester 2 prior to processing is shown in Table 6.The additives were melt-blended with PCT in a Prism twin screw extruder.The resulting material was extruded into a strand and then pelletizedprior to evaluation. The pelletized material was then tested for color,inherent viscosity, and CEG. After aging in a forced air oven for 3 h at200° C., the pellets were tested again to measure the aged properties.The color of the pellets was measured using a CieLAB colorimeter and thecolor was tracked with the b* value.

TABLE 6 Properties of PCT base materials Carboxyl Run End initial NumberSample IV Groups b* 1 Polyester 0.772 15.6 4.0 2

The weight percentages of components of the compositions used in theexperimental design is listed in Table 7. A control material (Run #1)was made where the Polyester 2 was passed thru the extruder with noadditives to show the effect of ageing on PCT with no stabilizer added.The results from evaluation of the different blends are shown in Table8.

TABLE 7 Polyester 2 with Irganox 1010 ™, Irgafos 168 ™ and Joncryl4468 ™ COMPOSITIONS (WEIGHT %) Run Irganox Irgafos Joncryl PolyesterNumber 1010 ™ 168 ™ 4468 ™ 2 1 0.00 0.00 0.00 100.00 2 0.63 0.38 0.5098.49 3 0.25 0.50 0.75 98.50 4 0.25 0.50 0.25 99.00 5 0.25 0.25 0.7598.75 6 1.00 0.25 0.25 98.50 7 1.00 0.50 0.25 98.25 8 1.00 0.25 0.7598.00 9 0.25 0.25 0.25 99.25 10 0.63 0.38 0.50 98.49 11 1.00 0.50 0.7597.75 12 0.63 0.38 0.50 98.49

TABLE 8 Polyester 2 with Irganox 1010 ™, Irgafos 168 ™ and Joncryl4468 ™—GPC, Inherent Viscosity and Carboxyl End Groups—Oven Aging at200° C. for 3 hours Responses Run CarboxylEnd INITIAL FINAL Delta NumberMn Mw Mz PD IV Groups (CEG) b* b* b* 1 10032 20589 35417 2.052 0.71424.37 6.76 12.38 5.62 2 10991 33864 134160 3.081 0.847 11.47 3.50 6.943.44 3 11015 34897 137446 3.168 0.914 6.59 1.69 3.21 1.52 4 10620 2681478979 2.525 0.784 15.09 2.91 5.53 2.62 5 10824 33581 129184 3.102 0.9089.03 1.87 4.27 2.40 6 10730 26171 73727 2.439 0.762 17.23 6.26 10.133.87 7 10638 28144 88882 2.646 0.757 15.81 6.68 10.93 4.25 8 11241 35473136575 3.156 0.934 5.98 4.03 5.78 1.75 9 10815 26587 78361 2.458 0.77615.58 3.17 4.72 1.55 10 11161 33821 133966 3.030 0.860 10.50 3.17 5.342.17 11 11390 36010 142339 3.162 0.949 5.73 2.26 3.88 1.62 12 1121433945 133949 3.027 0.857 10.66 3.09 5.49 2.40

The results from testing the compositions (Table 8) defined in theexperimental design were analyzed using a statistical software tool. Thesoftware was able to analyze experimental data and to assess themagnitude of the response provided by each additive, create models, andto describe the precision by which the models were able to analyze howchanges in composition would affect the responses. Additionally, thesoftware is able to confirm the optimal combination of additives thatwould provide the best performance during aging. A summary of theanalysis is shown in Table 4. The statistical software used was DESIGNEXPERT™ 8 software that is commercially available under the name DesignExpert by Stat Ease Inc., Hennepin Square, Suite 191, 2021 East HennepinAvenue, Minneapolis, Minn. 55413-2723 U.S.A. However, it is believedthat other commercially available statistical software could also beused.

TABLE 9 Summarized results Individual contributions InteractionsIrganox ™ Irgafos ™ Joncryl ™ Irganox ™* Irganox ™* Irgafos ™* Response1010 168 4468 Irgafos ™ Joncryl ™ Joncryl ™ R² IV + + 0.99 CEG − − −0.94 Initial b* + − − 0.89 Aged b* + + − − 0.94 For IV, + effect isdesired; For CEG, − effect is desired, for initial and aged b*, − effectis desired.

Models for each response were created by using Design Expert. The modelsevaluate how a specific response from the selected target criteriaproperties is affected by the individual components in each polymercomposition using the experimental data. In the case of IV, the responseof IV can be predicted with the following equation:

For FIG. 7:

IV=0.73−0.06*[Irganox™ 1010]+0.23*[Joncryl™ 4468]+0.14*[Irganox™1010]*[Joncryl 4468]

R²=0.99; R² _(adj)=0.99; R² _(pred)=0.98

The equation shows that the response of IV is directly impacted by theconcentrations of primary antioxidant and chain extender individually,but is also affected by the interaction of primary antioxidant and chainextender. The correlation coefficients (R²) are very high for thisresponse.

In the case of carboxyl chain ends (CEG), the response of CEG can beanalyzed with the following equation:

For FIG. 8:

CEG=19.8+3.7*[Irganox™1010] −4.6*[Irgafos™168]-13.0*[Joncryl™4468]−8.4*[Irganox 1010]*[Joncryl 4468]

R²=0.99; R² _(adj)=0.98; R² _(pred)=0.94

The response of CEG is directly impacted by the concentrations ofprimary antioxidant, secondary antioxidant, and chain extenderindividually, but is also affected by the interaction of primaryantioxidant and chain extender. The correlation coefficients (R²) arevery high for this response.

In the case of initial b* color (b*o), the response of b*o can beanalyzed with the following equation:

For FIG. 9:

b* ₀=2.1+5.91*[Irganox™ 1010] −1.1*[Joncryl™4468]−5.51*[Irganox™1010]*[Joncryl™4468]

R²=0.92; R² _(adj)=0.89; R² _(pred)=0.75

The response of b*₀ is thus directly impacted by the concentrations ofprimary antioxidant and chain extender individually, but is alsoaffected by the interaction of primary antioxidant and chain extender.The correlation coefficients (R²) are very high for this response.

In the case of final or aged b* color (b*f), the response of b*f can beanalyzed with the following equation:

For FIG. 10:

b* _(f)=0.34+10.1*[Irganox™ 1010]+7.8*[Irgafos™168] +7.0*[Joncryl™4468]−11.5*[Irganox™1010]*[Joncryl™4468] −18.3*[Irgafos™168]*[Joncry™|b 4468]

R²=0.97; R² _(adj)=0.94; R² _(pred)=0.93

The response of b*_(f) is directly impacted by the concentrations ofprimary antioxidant, secondary antioxidant, and chain extenderindividually, but is also affected by the interaction of primaryantioxidant and chain extender and by the interaction of secondaryantioxidant and chain extender. The correlation coefficients (R²) arevery high for this response.

Since one of the benefits of this invention is to achieve optimalthermal stability of the polyester, the overall composition can beoptimized to provide the most stable range of compositions. The DesignExpert software can be used to help evaluate optimal ranges by using aDesirability Function. Desirability is an objective function that rangesfrom zero outside of the limits to one at the goal. The numericaloptimization establishes a point that maximizes the desirabilityfunction. The characteristics of a goal may be altered by adjusting theweight or importance based upon selected overall target criteria.

For several responses and factors, all goals were combined into onedesirability function. Myers and Montgomery (Response SurfaceMethodology, p. 244) describe a multiple response method calleddesirability. The method makes use of an objective function, D(X),called the desirability function. It reflects the desirable ranges foreach response (di). The desirable ranges are from zero to one (least tomost desirable, respectively). The simultaneous objective function is ageometric mean of all transformed responses:

$D = {( {d_{1} \times d_{2} \times \ldots \times d_{n}} )^{\frac{1}{n}} = ( {\prod\limits_{i = 1}^{n}\; d_{i}} )^{\frac{1}{n}}}$

where n is the number of responses in the measure. If any of theresponses or factors fall outside their desirability range, the overallfunction becomes zero.

For certain polymers of this invention, the Desired Composition wasselected using the following criteria:

-   -   1. Stable or unchanging IV (or molecular weight)    -   2. Low CEG    -   3. Low initial b*    -   4. Low aged b*

Based on these criteria, Design Expert determined the desirability whichis shown in the contour plot of FIG. 11: Optimized composition (Irganox™1010=0.25%, Irgafos™ 168=0.50%, Joncryl™ 4468=0.65%,desirability=0.757).

These contour plots provide a range of compositions based on data inputinto the software from the compositions previously tested to meet thetarget criteria. Another way to evaluate the invention is with a contouroverlay plot. In a contour overlay plot, the range of propertiesachieved as specific parts of the composition, changes can be seen.Contour overlay plots are shown in FIGS. 12 and 13 herein.

From this analysis, a few conclusions can be made: (1) the accuracy(measured with adjusted R²) for this experiment is very good; (2) thereis a strong interaction between the Joncryl™ additive and the Irganox™additive across all responses; (3) For IV and CEG responses, high IV andlow CEG are achieved when Joncryl™4468 concentration is high and theIrganox™1010 concentration is high; (4) for color aging, the lowest b*was obtained for initial b* and aged b* measurements when the amount ofchain extending agent, Joncryl™4468 additive, was high and when theamount of secondary antioxidant, Irganox 1010™ additive, was low. and(5) there is a significant interaction between the described Joncryl™and Irganox™ additives for IV and CEG, but even more pronounced withcolor and color stability.

The target criteria list of properties was established to create acombination of additives that reduce color and color development whilemaintaining mechanical properties using inherent viscosity as a proxy.Based on these targets and the results from the DOE, an optimizedformulation was calculated (based on the selected target criteria)(Table 10):

TABLE 10 Optimized Formulation of Additives to reduce CEG and b* andincrease IV Additive Composition Joncryl ™ 4468 0.65% Irganox ™10100.25% Irgafos ™168 0.50%

Comparative Example #1 (Polyester 2)

A sample composition was made using different chain extender anddifferent secondary antioxidant. The composition is shown below. Testingof the resulting material showed very high CEG and very high b* comparedwith a similar composition described by the invention. Araldite ECN 1299(CAS#29690-82-2) is an epoxy novolac resin made by Huntsman AdvancedMaterials, in The Woodlands, Tex.; Ultranox 626, (CAS #26741-53-7), is abis (2,4-di-t-butylphenyl) pentaerythritol diphosphate made by Addivant,Danbury, Conn.

Araldite ™ Irganox ™ Ultranox ™ ECN Polyester Initial 1010 626 1299 #2IV CEG b* 0.5% 0.5% 0.5% 98.5% 0.73 19.5 21.7

It can be clearly seen from a comparison of the data in the aboverelevant working examples that a combination of primary antioxidant,secondary antioxidant and chain extending agent useful in the inventioncan improve thermal oxidative stability, color and/or flow of certainpolymers.

The invention has been described in detail with reference to theembodiments described herein, but it will be understood that variationsand modifications can be affected within the scope of the invention.

1. A polymer composition comprising: (A) at least one condensationpolymer comprising at least one diol residue, and (B) a stabilizercomposition comprising: (1) at least one primary antioxidant comprisingat least one phenolic antioxidant; and (2) at least one secondaryantioxidant comprising at least one phosphite, and (3) at least onechain extending agent; wherein the Δb* value for said polymercomposition is less than 10 according to the L*, a* and b* color systemof the CIE (International Commission on Illumination) after being heatedfor at least three hours at 200° C. or after being heated for at leasttwenty-four hours at 175° C.
 2. The polymer composition according toclaim 1, wherein the at least one diol residue comprises1,4-cyclohexanedimethanol (CHDM) residues.
 3. The polymer compositionaccording to claim 1, wherein the at least one primary antioxidant is ahindered phenolic antioxidant.
 4. The polymer composition according toclaim 3, wherein at least one hindered phenolic antioxidant ispentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.5. The polymer composition according to claim 1, wherein the phenolicantioxidant is present in an amount from 0.10 to 2.0 weight %, based onthe total weight of the polymer composition equaling 100 weight %. 6.The polymer composition according to claim 1, wherein the at least onephosphite antioxidant is tris(2,4-di-tert-butylphenyl)phosphite.
 7. Thepolymer composition according to claim 1, wherein the phosphiteantioxidant is present in an amount from 0.10 weight % to 1 weight %,based on the total weight of the polymer composition.
 8. The polymercomposition according to claim 1, wherein the weight ratio of phenolicantioxidant (1) to phosphite antioxidant (2) is from 1.1:1 to 3:1. 9.The polymer composition according to claim 1, wherein the at least onechain extending agent is selected from copolymers of glycidylmethacrylate with alkenes, copolymers of glycidyl methacrylate withalkenes and acrylic esters, copolymers of glycidyl methacrylate withalkenes and vinyl acetate, copolymers of glycidyl methacrylate andstyrene, and wherein the at least one chain extending agent has anaverage of greater than or equal to 4 pendant epoxy groups per molecule.10. (canceled)
 11. The polymer composition according to claim 1, whereinthe chain extending agent comprises a copolymer of glycidyl methacrylatewith styrene.
 12. The polymer composition according to claim 1, whereinthe at least one chain extending agent is present in an amount from 0.10weight % to 1 weight %, based on the total weight of the polymercomposition.
 13. The polymer composition according to claim 1, whereinthe weight ratio of chain extending agent to primary antioxidant is from1:1.1 to 1:3.
 14. The polymer composition according to claim 1, whereinthe polymer composition has an inherent viscosity in the range from 0.35to 1.0 dL/g, as determined in 60/40 (wt/wt) phenol/tetrachloroethane ata concentration of 0.5 g/100 ml at 25° C.
 15. The polymer compositionaccording to claim 1, wherein the at least one phenolic antioxidant ispentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,the at least one phosphite is tris(2,4-di-tert-butylphenyl)phosphite,and the at least one chain extending agent is Joncryl™4468 additive. 16.The polymer composition according to claim 1, wherein the polymercomposition comprise: (1) at least one phenolic antioxidant in theamount of from 0.01 weight % to 2.0 weight %, (2) at least one phosphitein the amount of from 0.01 weight % to 2.0 weight %, and (3) at leastone chain extending agent in the amount of from 0.01 weight % to 2.0weight percent, based on the total weight of the polymer composition.17. The polymer composition according to claim 1, wherein thecondensation polymer is amorphous.
 18. The polymer composition accordingto claim 1, wherein the condensation polymer is a polyester comprisingat least one dicarboxylic acid or an ester thereof and at least onediol, wherein the total of acid residues present is 100 mole % andwherein the total of diol residues present is 100 mole %, wherein thedicarboxylic acid or ester thereof component comprises residues of1,4-cyclohexanedicarboxylic acid or an ester thereof, and wherein thediol component comprises residues of 1,4-cyclohexanedimethanol andpolytetramethylene ether glycol.
 19. The polymer composition accordingto any of claim 1, wherein the polymer is selected from at least onepolyester comprising: (a) diacid residues comprising from about 70 toabout 100 mole percent of terephthalic acid (TPA) residues and 0 toabout 30 mole percent isophthalic acid (IPA) residues; and (b) diolresidues comprising from about 20 to about 100 mole percent of1,4-cyclohexanedimethanol (CHDM) residues and 0 to 100 mole percent ofethylene glycol; wherein the total of diacid residues is 100 mole % andwherein the total of diol residues is 100 mole %.
 20. The polymercomposition according to claim 1, wherein the polymer is acopolyesterether.
 21. (canceled)
 22. The polymer composition accordingto claim 18, having an inherent viscosity of from about 0.7 to about 1.5dL/g, as determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C., and comprising: A. adicarboxylic acid component consisting essentially of1,4-cyclohexanedicarboxylic acid, B. a glycol component consistingessentially of (1) 1,4-cyclohexanedimethanol, and (2) from about 15 toabout 50 weight percent, or from 20 to 35 weight percent, based on theweight of the polyesterether, of polytetramethyleneether glycol having aweight molecular weight of about 500 to about 2000.